Catalysts and methods for catalytic oxidation

ABSTRACT

Catalytic systems and methods for oxidizing materials in the presence of metal catalysts (preferably manganese-containing catalysts) complexed with selected macropolycyclic rigid ligands, preferably cross-bridged macropolycyclic ligands. Included are using these metal catalysts in such processes as: synthetic organic -oxidation reactions such as oxidation of organic functional groups, hydrocarbons, and heteroatoms, including enantiomeric epoxidation of alkenes, enynes, sulfides to sulfones and the like; oxidation of oxidizable compounds (e.g., stains) on surfaces such as fabrics, dishes, countertops, dentures and the like; oxidation of oxidizable compounds in solution, dye transfer inhibition in the laundering of fabrics; and further in the bleaching of pulp and paper products.

CROSS-REFERENCE

[0001] This application claims priority under 35 U.S.C. §120 to U.S.application Ser. No. 09/380,672, filed Sep. 7, 1999, which is an entryinto the U.S. National Stage under 35 U.S.C. §371 of PCT InternationalApplication Serial No. PCT/IB98/00302, filed Mar. 6, 1998, which claimspriority under PCT Article 8 and 35 U.S.C. §119(e) to U.S. ProvisionalApplication Serial No. 60/040,629, filed Mar. 7, 1997.

TECHNICAL FIELD

[0002] The present invention relates to catalytic systems and methodsfor oxidizing materials in the presence of catalysts which are complexesof transition metals such as Mn, Fe or Cr, with selected macropolycyclicrigid ligands, preferably cross-bridged macropolycyclic ligands. Morespecifically, the present invention relates to catalytic oxidation ofoxidizable compounds using said metal catalysts, including syntheticorganic oxidation reactions as appropriate to chemical process industry,drug synthesis, and the preparation of specialty chemicals, such asenantiomeric epoxidation of alkenes, oxidation of organic functionalgroups, hydrocarbons, heteroatoms, or enynes, conversion of sulfides tosulfones, and the like; oxidation of oxidizable compounds (e.g., stains)on surfaces such as fabrics, dishes, countertops, dentures and the like;oxidation of oxidizable compounds in solution; dye transfer inhibitionin the laundering of fabrics; the decontamination of soils; and further,to the bleaching of pulp and paper. Preferred catalytic systems includetransition-metal complexes of ligands which are polyazamacropolycycles,especially including specific azamacrobicycles, such as cross-bridgedderivatives of cyclam.

BACKGROUND OF THE INVENTION

[0003] A damaging effect of manganese on fabrics during bleaching hasbeen known since the 19th century. In the 1960's and '70's, efforts weremade to include simple Mn(II) salts in detergents, but none sawcommercial success. More recently, metal-containing catalysts containingmacrocyclic ligands have been described for use in bleachingcompositions. Such catalysts include those described asmanganese-containing derivatives of small macrocycles, especially1,4,7-trimethyl-1,4,7-triazacyclononane. These catalysts assertedlycatalyze the bleaching action of peroxy compounds against variousstains. Several are said to be effective in washing and bleaching ofsubstrates, including in laundry and cleaning applications and in thetextile, paper and wood pulp industries. However, such metal-containingbleach catalysts, especially these manganese-containing catalysts, stillhave shortcomings, for example a tendency to damage textile fabric,relatively high cost, high color, and the ability to locally stain ordiscolor substrates.

[0004] Salts of cationic-metal dry cave complexes have been described inU.S. Pat. No. 4,888,032, to Busch, Dec. 19, 1989 as complexing oxygenreversibly, and are taught as being useful for oxygen scavenging andseparating oxygen from air. A wide variety of ligands are taught to beusable, some of which include macrocycle ring structures and bridginggroups. See also: D. H. Busch, Chemical Reviews, (1993), 93, 847-880,for example the discussion of superstructures on polydentate ligands atpages 856-857, and references cited therein, as well as B. K. Coltrainet al., “Oxygen Activation by Transition Metal Complexes ofMacrobicyclic Cyclidene Ligands” in “The Activation of Dioxygen andHomogeneous Catalytic Oxidation”, Ed. by E. H. R. Barton, et al. (PlenumPress, NY; 1993), pp. 359-380.

[0005] More recently the literature on azamacrocycles has grown at arapid pace. Among the many references are Hancock et. al., J. Chem.Soc., Chem. Commun., (1987), 1129-1130; Weisman et al., “Synthesis andTransition Metal Complexes of New Cross-Bridged Tetraamine Ligands”,Chem. Commun., (1996), 947-948; U.S. Pat. Nos. 5,428,180, 5,504,075, and5,126,464, all to Burrows et al.; 5,480,990, to Kiefer et al.; and5,374,416, to Rousseaux et al.

[0006] Homogeneous transition metal catalysis is a broad realm that hasenjoyed intensive activity leading to a number of large scale chemicalprocesses; e.g., the Monsanto acetic acid process, the Dupontadiponitrile process, and others, among which certain famous onesinvolve oxidations (Wacker Process, Midcentury Process). Further,transition metal oxidation catalysis has been promoted heavily instudies on the biomimicry of the monooxygenase enzymes, especiallycytochrome P450. Whereas such studies have emphasized and shown theprowess of the native porphyrin prosthetic group, others have shown thatcertain oxidative capabilities exist in the same metal ions in thesimple solvated condition. This history reveals the possibility thatcatalytic oxidation may alter almost all families of organic compoundsto yield valuable products, but successful applications depend on theactivity of the putative catalyst, it survivability under reactionconditions, its selectivity, and the absence of undesirable sidereactions or over-reaction.

[0007] It has now surprisingly been determined that the use of certaintransition-metal catalysts of specific rigid macropolycycles, preferablycontaining cross-bridging, have exceptional kinetic stability such thatthe metal ions only dissociate very slowly under conditions which woulddestroy complexes with ordinary ligands, and further have exceptionalthermal stability. Thus, the present invention catalyst systems canprovide one or more important benefits. These include improvedeffectiveness and in some instances even synergy with one or moreprimary oxidants such as hydrogen peroxide, hydrophilically orhydrophobically activated hydrogen peroxide, preformed peracids,monopersulfate or hypochlorite; the ability to be effective catalysts,some, especially those containing Mn(II), having little to no color andallowing great formulation flexibility for use in consumer productswhere product aesthetics are very important; and effectiveness on avariety of substrates and reactants, including a variety of soiled orstained fabrics or hard surfaces while minimizing tendency to stain ordamage such surfaces.

[0008] Therefore, the present invention provides improved catalyticsystems containing transition-metal oxidation catalysts, and methodswhich utilize these catalysts and catalytic systems in the area ofchemical syntheses involving organic oxidation reactions, such asoxidation of organic functional groups, hydrocarbons, or heteroatoms,and epoxidation of alkenes; oxidation of oxidizable stains on fabricsand hard surfaces; oxidation of reactants in solutions; pulp and paperbleaching; the oxidation of organic pollutants and for other equivalenthighly desirable purposes.

[0009] These and other objects are secured herein, as will be seen fromthe following disclosures.

BACKGROUND ART

[0010] Transition metals such as manganese are well-known in oxidationsystems. Free Mn⁺² ions have, for example, been implicated in theoxidation of lignin by white rot mycetes. Manganese and other transitionmetals in complexed form are familiar in biological systems with avariety of ligands. See, for example, “The Biological Chemistry of theElements”, J. J. R. Fraustro da Silva and R. J. P. Williams, ClarendonPress, Oxford, reprinted 1993. Complexes of ligands such as substitutedporphyrins with iron, manganese, chromium or ruthenium are asserted tobe useful in catalyzing a variety of oxidative reactions, includingoxidation of lignin and industrial pollutants. See, for example, U.S.Pat. No. 5,077,394.

[0011] A recent review of nickel-catalyzed oxidations includes thefollowing disclosures: (1) simple tetradentate ligands such as cyclam (anon-cross-bridged, N-H functional tetraazamacrocycle) or salen (afour-donor N,N,O,O ligand) render Ni(II) active for olefin epoxidation;(2) Ni salen complexes can utilize sodium hypochlorite as primaryoxidant and show high catalytic turnover in epoxidation reactions; (3)bleach can be used under phase-transfer conditions for manganeseporphyrin-catalyzed epoxidations and can be adapted to Ni as well; and(4) reactivity is dramatically influenced by pH with conversion ofstyrenes into epoxides being quantitative under conditions said to beoptimized at pH 9.3.

[0012] The catalysis of oxidation reactions by transition metals is moregenerally useful in synthetic organic chemistry in such varied aspectsof the chemical process industry as commodity chemical production anddrug manufacture, in addition to the laboratory, and also in consumerproduct applications such as detergency. Laundry bleaching in general isreviewed in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd and4th editions under a number of headings including “Bleaching Agents”,“Detergents” and “Peroxy Compounds”. Laundry applications of bleachingsystems include the use of amido-derived bleach activators in laundrydetergents as described in U.S. Pat. No. 4,634,551. The use of manganesewith various ligands to enhance bleaching is reported in the followingUnited States patents: U.S. Pat. Nos. 4,430,243; 4,728,455; 5,246,621;5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,117;5,274,147; 5,153,161; 5,227,084; 5,114,606; 5,114,611. See also: EP549,271 A1; EP 544,490 A1; EP 549,272 A1; and EP 544,440 A2.

[0013] U.S. Pat. No. 5,580,485 describes a bleach and oxidation catalystcomprising an iron complex having formula A[LFeX_(n)]^(z)Y_(q)(A) orprecursors thereof. The most preferred ligand is said to beN,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine, N₄Py. TheFe-complex catalyst is said to be useful in a bleaching systemcomprising a peroxy compound or a precursor thereof and suitable for usein the washing and bleaching of substrates including laundry,dishwashing and hard surface cleaning. Alternatively, the Fe-complexcatalyst is assertedly also useful in the textile, paper and wood-pulpindustries.

[0014] The art of the transition metal chemistry of macrocycles isenormous; see, for example “Heterocyclic compounds: Aza-crownmacrocycles”, J. S. Bradshaw et. al., Wiley-Interscience, 1993 whichalso describes a number of syntheses of such ligands. See especially thetable beginning at p. 604. U.S. Pat. No. 4,888,032 describes salts ofcationic metal dry cave complexes.

[0015] Cross-bridging, i.e., bridging across nonadjacent nitrogens, ofcyclam (1,4,8,11-tetraazacyclotetradecane) is described by Weisman etal, J. Amer. Chem. Soc., (1990), 112(23), 8604-8605. More particularly,Weisman et al., Chem. Commun., (1996), pp. 947-948 describe newcross-bridged tetraamine ligands which are bicyclo[6.6.2], [6.5.2], and[5.5.2] systems, and their complexation to Cu(II) and Ni(II)demonstrating that the ligands coordinate the metals in a cleft.Specific complexes reported include those of the ligands 1.1:

[0016] in which A is hydrogen or benzyl and (a) m=n=1; or (b) m=1 andn=0; or (c) m=n=0, including a Cu(II)chloride complex of the ligandhaving A=H and m=n=1; Cu(II) perchlorate complexes where A=H and m—n=1or m=n=0; a Cu(II)chloride complex of the ligand having A=benzyl andm=n=0; and a Ni(II)bromide complex of the ligand having A=H and m=n=1.In some instances halide in these complexes is a ligand, and in otherinstances it is present as an anion. This handful of complexes appearsto be the total of those known wherein the cross-bridging is not across“adjacent” nitrogens.

[0017] Ramasubbu and Wainwright, J. Chem. Soc., Chem. Commun., (1982),277-278 in contrast describe structurally reinforcing cyclen by bridgingadjacent nitrogen donors. Ni(II) forms a pale yellow mononucleardiperchlorate complex having one mole of the ligand in a square planarconfiguration. Kojima et al, Chemistry Letters, (1996), pp. 153-154,describes assertedly novel optically active dinuclear Cu(II) complexesof a structurally reinforced tricyclic macrocycle.

[0018] Bridging alkylation of saturated polyaza macrocycles as a meansfor imparting structural rigidity is described by Wainwright, Inorg.Chem., (1980), 19(5), 1396-8. Mali, Wade and Hancock describe a cobalt(III) complex of a structurally reinforced macrocycle, see J. Chem.Soc., Dalton Trans., (1992), (1), 67-71. Seki et al describe thesynthesis and structure of chiral dinuclear copper(II) complexes of anassertedly novel reinforced hexaazamacrocyclic ligand; see Mol. Cryst.Lig. Cryst. Sci. Technol., Sect. A (1996), 276, 79-84; see also relatedwork by the same authors in the same Journal at 276, 85-90 and 278,235-240.

[0019] [Mn(III)₂(μ-O)(μ-O₂CMe)₂L2]²⁺ and [Mn(IV)₂(μ-O)₃L₂]²⁺ complexesderived from a series of N-substituted 1,4,7-triazacyclononanes aredescribed by Koek et al., see J. Chem. Soc., Dalton Trans., (1996),353-362. Important earlier work by Wieghardt and co-workers on1,4,7-triazacyclononane transition metal complexes, including those ofManganese, is described in Angew. Chem. Internat. Ed. Engl., (1986), 25,1030-1031 and J. Amer. Chem. Soc., (1988), 110, 7398.

[0020] Ciampolini et al., J. Chem. Soc., Dalton Trans., (1984),1357-1362 describe synthesis and characterization of the macrocycle1,7-dimethyl-1,4,7,10-tetraazacyclododecane and of certain of its Cu(II)and Ni(II) complexes including both a square-planar Ni complex and acis-octahedral complex with the macrocycle co-ordinated in a foldedconfiguration to four sites around the central nickel atom. Hancock etal, Inorg. Chem., (1990), 29, 1968-1974 describe ligand designapproaches for complexation in aqueous solution, including chelate ringsize as a basis for control of size-based selectivity for metal ions.Thermodynamic data for macrocycle interaction with cations, anions andneutral molecules is reviewed by Izatt et al., Chem. Rev., (1995), 95,2529-2586 (478 references).

[0021] Bryan et al, Inorg. Chem., (1975), 14(2)., 296-299 describesynthesis and characterization of Mn(II) and Mn(II) complexes ofmeso-5,5,7-12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane([14]aneN4]. The isolated solids are assertedly frequently contaminatedwith free ligand or “excess metal salt” and attempts to prepare chlorideand bromide derivatives gave solids of variable composition which couldnot be purified by repeated crystallization.

[0022] Costa and Delgado, Inorg. Chem., (1993), 32, 5257-5265, describemetal complexes such as the Co(II), Ni(II) and Cu(II) complexes, ofmacrocyclic complexes containing pyridine. Derivatives of thecross-bridged cyclens, such as salts of4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane, are describedby Bencini et al., see Supramolecular Chemistry, 3, 141-146. U.S. Pat.No. 5,428,180 and related work by Cynthia Burrows and co-workers in U.S.Pat. Nos. 5,272,056 and 5,504,075 describe pH dependence of oxidationsusing cyclam or its derivatives, oxidations of alkenes to epoxides usingmetal complexes of such derivatives, and pharmaceutical applications.Hancock et al., Inorganica Chimica Acta., (1989), 164, 73-84 describeunder a title including “complexes of structurally reinforcedtetraaza-macrocyclic ligands of high ligand field strength” thesynthesis of complexes of low-spin Ni(II) with three assertedly novelbicyclic macrocycles. The complexes apparently involve nearly coplanararrangements of the four donor atoms and the metals despite the presenceof the bicyclic ligand arrangement. Bencini et al., J. Chem. Soc., Chem.Commun., (1990), 174-175 describe synthesis of a small aza-cage,4,10-dimethyl-1,4,7,10-15-pentaazabicyclo[5.5.5]heptadecane, which“encapsulates” lithium. Hancock and Martell, Chem. Rev., (1989), 89,1875-1914 review ligand design for selective complexation of metal ionsin aqueous solution. Conformers of cyclam complexes are discussed onpage 1894 including a folded conformer -see FIG. 18(cis-V). The paperincludes a glossary. In a paper entitled “Structurally ReinforcedMacrocyclic Ligands that Show Greatly Enhanced Selectivity for MetalIons on the Basis of the Match and Size Between the Metal Ion and theMacrocyclic Cavity”, Hancock et al., J. Chem. Soc., Chem. Commun.,(1987), 1129-1130 describe formation constants for Cu(II), Ni(II) andother metal complexes of some bridged macrocycles having piperazine-likestructure.

[0023] Many other macrocycles are described in the art, including typeswith pedant groups and a wide range of intracyclic and exocyclicsubstituents. Although the macrocycle and transition metal complexliterature are, separately, vast, relatively little appears to have beenreported on how to select and combine specific transition metals andspecific macrocycle classes, for example cross-bridged tetraaza- andpenta-aza macrocycles, so as to apply them for the further improvementof oxidation catalysis. There is, for example, no apparent singling outof these materials from the vast chemical literature, either alone or astheir transition metal complexes, for use in bleaching detergents.

SUMMARY OF THE INVENTION

[0024] The present invention relates to a method for oxidizingmaterials, said method comprising contacting (preferably in the presenceof a solvent, such as water, non-aqueous solvents, and mixtures thereof)a material capable of being oxidized with an oxidation agent and atransition-metal oxidation catalyst, wherein said transition-metaloxidation catalyst comprises a complex of a transition metal selectedfrom the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II),Fe(II), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I),Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV),V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II),Ru(III), and Ru(IV), preferably Mn(II), Mn(III), Mn(IV), Fe(II),Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr(VI), preferablyMn, Fe and Cr in the (II) or (III) state, coordinated with amacropolycyclic rigid ligand, preferably a cross-bridged macropolycyclicligand, having at least 3 donor atoms, at least two of which arebridgehead donor atoms.

[0025] The present invention also relates to catalytic systems effectivefor oxidation of materials comprising: (a) a catalytically effectiveamount, preferably from about 1 ppb to about 99.9%, more typically fromabout 0.001 ppm to about 500 ppm, preferably from about 0.05 ppm toabout 100 ppm (wherein “ppb” denotes parts per billion by weight and“ppm” denotes parts per million by weight), of a transition-metaloxidation catalyst, wherein said transition-metal oxidation catalystcomprises a complex of a transition metal selected from the groupconsisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV),Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(II), Cu(I), Cu(II), Cu(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV)coordinated with a macropolycyclic rigid ligand, preferably across-bridged macropolycyclic ligand, having at least 3 donor atoms, atleast two of which are bridgehead donor atoms; and (b) the balance, to100%, of one or more adjunct materials.

[0026] Amounts of the essential transition-metal catalyst and essentialadjunct materials can vary widely depending on the precise application.For example, the catalytic systems herein may be provided as aconcentrate, in which case the catalyst can be present in a highproportion, for example 0.01%-80%, or more, of the composition. Theinvention also encompasses catalytic systems at their in-use levels;such systems include those in which the catalyst is dilute, for exampleat ppb levels. Intermediate level compositions, for example thosecomprising from about 0.01 ppm to about 500 ppm, more preferably fromabout 0.05 ppm to about 50 ppm, more preferably still from about 0.1 ppmto about 10 ppm of transition-metal catalyst and the balance to 100%,preferably at least about 0.1%, typically about 99% or more beingsolid-form or liquid-form adjunct materials (for example fillers,solvents, and adjuncts especially adapted to a particular use (forexample papermaking adjuncts, detergent adjuncts, or the like). Theinvention also encompasses a large number of novel transition-metalcatalysts per-se, especially including their substantially pure (100%active) forms.

[0027] The present invention preferably relates to catalytic systemseffective for oxidation of materials comprising: (a) a catalyticallyeffective amount, preferably from about 1 ppb to about 49%, of atransition-metal oxidation catalyst, said catalyst comprising a complexof a transition metal and a macropolycyclic rigid ligand, preferably across-bridged macropolycyclic ligand, wherein:

[0028] (1) said transition metal is selected from the group consistingof Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I),Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II),Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V),Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(II), and Ru(IV);

[0029] (2) said macropolycyclic rigid ligand is coordinated by at leastthree, preferably at least four, more preferably four or five, donoratoms to the same transition metal and comprises:

[0030] (i) an organic macrocycle ring containing three, preferably four,or more donor atoms (preferably at least 3, more preferably at least 4,of these donor atoms are N) separated from each other by covalentlinkages of at least one, preferably 2 or 3, non-donor atoms, two tofive (preferably three to four, more preferably four) of these donoratoms being coordinated to the same transition metal in the complex;

[0031] (ii) a linking moiety, preferably a cross-bridging chain, whichcovalently connects at least 2 (preferably non-adjacent) donor atoms ofthe organic macrocycle ring, said covalently connected (preferablynon-adjacent) donor atoms being bridgehead donor atoms which arecoordinated to the same transition metal in the complex, and whereinsaid linking moiety (preferably a cross-bridged chain) comprises from 2to about 10 atoms (preferably the cross-bridged chain is selected from2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donoratom), including for example, a cross-bridge which is the result of aMannich condensation of ammonia and formaldehyde; and

[0032] (iii) optionally, one or more non-macropolycyclic ligands,preferably monodentate ligands, such as those selected from the groupconsisting of H₂O, ROH, NR₃, RCN, OH⁻, OOH⁻, RS⁻, RO⁻, RCOO⁻, OCN⁻,SCN⁻, N₃ ⁻, CN⁻, F⁻, Cl⁻, Br⁻, I⁻, O₂ ⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ²⁻, SO₃ ²⁻,PO₄ ³⁻, organic phosphates, organic phosphonates, organic sulfates,organic sulfonates, and aromatic N donors such as pyridines, pyrazines,pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles andthiazoles with R being H, optionally substituted alkyl, optionallysubstituted aryl (specific examples of monodentate ligands includingphenolate, acetate or the like); and

[0033] (b) at least about 0.1%, preferably B %, of one or more adjunctmaterials (where B %, the “balance” of the composition expressed as apercentage, is obtained by subtracting the weight of said component (a)from the weight of the total composition and then expressing the resultas a percentage by weight of the total composition).

[0034] The present invention also preferably relates to catalyticsystems effective for oxidation of materials comprising: (a) acatalytically effective amount, as identified supra, of atransition-metal oxidation catalyst, said catalyst comprising a complexof a transition metal and a macropolycyclic rigid ligand (preferably across-bridged macropolycyclic ligand) wherein: (1) said transition metalis selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),Cu(I), Cu(II), Cu(III), Cr(II), Cr(II), Cr(IV), Cr(V), Cr(VI), V(III),V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II),Ru(II), and Ru(IV), and (2) said macropolycyclic rigid ligand isselected from the group consisting of: (i) the macropolycyclic rigidligand of formula (I) having denticity of 3 or 4:

[0035] (ii) the macropolycyclic rigid ligand of formula (II) havingdenticity of 4 or 5:

[0036] (iii) the macropolycyclic rigid ligand of formula (IV) havingdenticity of 5 or 6:

[0037] (iv) the macropolycyclic rigid ligand of formula (IV) havingdenticity of 6 or 7:

[0038] wherein in these formulas:

[0039] each “E” is the moiety (CR_(n))_(a)—X—(CR_(n))_(a′), wherein X isselected from the group consisting of O, S, NR and P, or a covalentbond, and preferably X is a covalent bond and for each E the sum of a+a′is independently selected from 1 to 5, more preferably 2 and 3;

[0040] each “G” is the moiety (CR_(n))_(b);

[0041] each “R” is independently selected from H, alkyl, alkenyl,alkynyl, aryl, alkylaryl (e.g., benzyl), and heteroaryl, or two or moreR are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,or heterocycloalkyl ring;

[0042] each “D” is a donor atom independently selected from the groupconsisting of N, O, S, and P, and at least two D atoms are bridgeheaddonor atoms coordinated to the transition metal (in the preferredembodiments, all donor atoms designated D are donor atoms whichcoordinate to the transition metal, in contrast with heteroatoms in thestructure which are not in D such as those which may be present in E;the non-D heteroatoms can be non-coordinating and indeed arenon-coordinating whenever present in the preferred embodiment);

[0043] “B” is a carbon atom or “D” donor atom, or a cycloalkyl orheterocyclic ring;

[0044] each “n” is an integer independently selected from 1 and 2,completing the valence of the carbon atoms to which the R moieties arecovalently bonded;

[0045] each “n′” is an integer independently selected from 0 and 1,completing the valence of the D donor atoms to which the R moieties arecovalently bonded;

[0046] each “n″” is an integer independently selected from 0, 1, and 2completing the valence of the B atoms to which the R moieties arecovalently bonded;

[0047] each “a” and “a” is an integer independently selected from 0-5,preferably a+a′ equals 2 or 3, wherein the sum of all “a” plus “a” inthe ligand of formula (I) is within the range of from about 7 to about12, the sum of all “a” plus “a′” in the ligand of formula (II) is withinthe range of from about 6 (preferably 8) to about 12, the sum of all “a”plus “a” in the ligand of formula (III) is within the range of fromabout 8 (preferably 10) to about 15, and the sum of all “a” plus “a” inthe ligand of formula (IV) is within the range of from about 10(preferably 12) to about 18;

[0048] each “b” is an integer independently selected from 0-9,preferably 0-5 (wherein when b=0, (CR_(n))₀ represents a covalent bond),or in any of the above formulas, one or more of the (CR_(n))_(b)moieties covalently bonded from any D to the B atom is absent as long asat least two (CR_(n))_(b) covalently bond two of the D donor atoms tothe B atom in the formula, and the sum of all “b” is within the range offrom about 1 to about 5; and

[0049] (iii) optionally, one or more non-macropolycyclic ligands; and

[0050] (b) adjunct materials at suitable levels, as identifiedhereinabove.

[0051] The present invention also includes many novel transition-metalcomplexes which are useful oxidation catalysts. Such transition-metalcomplexes include: Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III),Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II),Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V),Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), andRu(IV), preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Cr(II),Cr(III), Cr(IV), Cr(V), and Cr(VI), more preferably the Mn(II), Mn(III),Mn(IV), Mn(V), Fe(II), Fe(III), Fe (IV), Cr(II) and Cr(III) complexes ofthe cross-bridged tetraazamacrocycles and cross-bridgedpentaazamacrocycles; these complexes include those in which thecross-bridging moiety is a C2-C4 alkyl moiety and in which there is amole ratio of macrocycle to metal of 1:1, and moreover these are mostpreferably monometallic mononuclear complexes, though in general,dimetallic or multimetallic complexes are not excluded.

[0052] To further illustrate, a preferred sub-group of the inventivetransition-metal complexes includes the Mn(II), Fe(II) and Cr(III)complexes of the ligand 1.2:

[0053] wherein m and n are integers from 0 to 2, p is an integer from 1to 6, preferably m and n are both 0 or both 1 (preferably both 1), or mis 0 and n is at least 1; and p is 1; and A is a nonhydrogen moietypreferably having no aromatic content; more particularly each A can varyindependently and is preferably selected from methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but notboth, of the A moieties is benzyl, and combinations thereof. In one suchcomplex, one A is methyl and one A is benzyl.

[0054] All parts, percentages and ratios used herein are expressed aspercent weight unless otherwise specified. All documents cited are, inrelevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

[0055] Catalytic Systems for Oxidizing Materials:

[0056] The catalytic systems of the present invention comprise aparticularly selected transition-metal oxidation catalyst which is acomplex of a transition metal and a macropolycyclic rigid ligand,preferably one which is cross-bridged; the catalytic systems preferablyalso comprise an oxidation agent or “primary oxidant”, preferably onewhich is a low cost, readily available substance producing little or nowaste, such as a source of hydrogen peroxide. The source of hydrogenperoxide can be H₂O₂ itself, its solutions, or any commonhydrogen-peroxide releasing salt, adduct or precursor, such as sodiumperborate, sodium percarbonate, or mixtures thereof. Also useful areother sources of available oxygen such as persulfate (e.g., OXONE,manufactured by DuPont), as well as preformed organic peracids and otherorganic peroxides. More generally, chlorine or other oxidants such asClO₂ or NaOCl can be used.

[0057] Mixtures of primary oxidants can be used; in such mixtures, anoxidant which is not present in major proportion can be used, forexample as in mixtures of a major proportion of hydrogen peroxide and aminor proportion of peracetic acid or its salts. In this example, theperacetic acid is termed the “secondary oxidant”. Secondary oxidants canbe selected from the same list of oxidants given hereinafter; the use ofsecondary oxidants is optional but may be highly desirable in certainembodiments of the invention. The catalytic system often furthercomprises further adjuncts, including compounds which liberate oxidantas a result of in-situ chemical reaction; as well as solvents and otheradditives characteristic of the end-use of the catalytic system. Tosecure the benefits of the invention, a substrate material, such as achemical compound to be oxidized, or a commercial mixture of materialssuch as a paper pulp, or a soiled material such as a textile containingone or more materials or soils to be oxidized, is added to the catalyticsystem under widely ranging conditions further described hereinafter.

[0058] The catalytic systems herein are useful for oxidative syntheticchemistry processes, such as oxidation of organic functional groups,hydrocarbons, heteroatoms, and epoxidation (including enantiomeric) ofalkenes and enynes, oxidation of sulfides to sulfones, and the like.

[0059] The present invention catalytic systems also have utility in thearea of oxidizing (preferably including bleaching) wood pulp for use in,for example, paper making processes. Other utilities include oxidativedestruction of waste materials or effluents.

[0060] Effective Amounts of Catalyst Materials

[0061] The term “catalytically effective amount”, as used herein, refersto an amount of the transition-metal oxidation catalyst present in thepresent invention catalytic systems, or during use according to thepresent invention methods, that is sufficient, under whatevercomparative or use conditions are employed, to result in at leastpartial oxidation of the material sought to be oxidized by the catalyticsystems or method. For example, in the synthesis of epoxides fromalkenes, the catalytic amount is that amount which is sufficient tocatalyze the desired epoxidation reaction. As noted, the inventionencompasses catalytic systems both at their in-use levels and at thelevels which may commercially be provided for sale as “concentrates”;thus “catalytic systems” herein include both those in which the catalystis highly dilute and ready to use, for example at ppb levels, andcompositions having rather higher concentrations of catalyst and adjunctmaterials. Intermediate level compositions, as noted in summary, caninclude those comprising from about 0.01 ppm to about 500 ppm, morepreferably from about 0.05 ppm to about 50 ppm, more preferably stillfrom about 0.1 ppm to about 10 ppm of transition-metal catalyst and thebalance to 100%, typically about 99% or more, being solid-form orliquid-form adjunct materials (for example fillers, solvents, andadjuncts especially adapted to a particular use, such as papermakingadjuncts, detergent adjuncts, or the like). In terms of amounts ofmaterials, the invention also encompasses a large number of noveltransition-metal catalysts per-se, especially including theirsubstantially pure (100% active) forms. Other amounts, for example ofoxidant materials and other adjuncts for specialized uses, areillustrated in more detail hereinafter.

[0062] Transition-Metal Oxidation Catalysts:

[0063] The present invention catalytic systems comprise atransition-metal oxidation catalyst. In general, the catalyst containsan at least partially covalently bonded transition metal, and bondedthereto at least one particularly defined macropolycyclic rigid ligand,preferably one having four or more donor atoms and which iscross-bridged or otherwise tied so that the primary macrocycle ringcomplexes in a folded conformation about the metal. Catalysts herein arethus neither of the more conventional macrocyclic type: e.g., porphyrincomplexes, in which the metal can readily adopt square-planarconfiguration; nor are they complexes in which the metal is fullyencrypted in a ligand. Rather, the presently useful catalysts representa selection of all the many complexes, hitherto largely unrecognized,which have an intermediate state in which the metal is bound in a“cleft”. Further, there can be present in the catalyst one or moreadditional ligands, of generally conventional type such as chloridecovalently bound to the metal; and, if needed, one or more counter-ions,most commonly anions such as chloride, hexafluorophosphate, perchlorateor the like; and additional molecules to complete crystal formation asneeded, such as water of crystallization. Only the transition-metal andmacropolycyclic rigid ligand are, in general, essential.

[0064] Transition-metal oxidation catalysts useful in the inventioncatalytic systems can in general include known compounds where theyconform with the invention definition, as well as, more preferably, anyof a large number of novel compounds expressly designed for the presentoxidation catalysis uses and non-limitingly illustrated by any of thefollowing:

[0065] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0066] Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0067] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate

[0068]Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

[0069] Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II) Hexafluorophosphate

[0070] Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

[0071] Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II) Tetrafluoroborate

[0072] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate

[0073]Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0074] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0075]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0076]Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0077]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0078] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneIron(II)

[0079] Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneIron(II)

[0080] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneCopper(II)

[0081] Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneCopper(II)

[0082] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneCobalt(II)

[0083] Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneCobalt(II)

[0084] Dichloro5,12-dimethyl—4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0085]Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0086]Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0087]Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0088]Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0089]Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0090]Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0091]Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0092]Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0093]Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0094]Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0095]Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0096]Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0097] Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)

[0098] Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)

[0099] Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II)

[0100] Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II)

[0101]Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethy1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0102]Aquo-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0103]Chloro-2-(2-hydroxybenzyl)-5-methy1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0104]Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecaneManganese(II)

[0105]Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Chloride

[0106] Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Chloride

[0107]Dichloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0108]Aquo-Chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0109]Aquo-Chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0110]Dichloro-5-(Trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Chloride

[0111]Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[8.5.2]heptadecaneManganese(II)

[0112]Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo[8.6.6]docosa-3(8),4,6-trieneManganese(II)

[0113] Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecane Manganese(II)

[0114] Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecaneManganese(II)

[0115] Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecaneManganese(II)

[0116]Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0117]Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0118] Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene manganese(II)Hexafluorophosphate

[0119]Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene Manganese(II)Trifluoromethanesulfonate

[0120]Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24), 11,13,15(25)-hexaene Iron(II)Trifluoromethanesulfonate

[0121]Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecaneManganese(II) Hexafluorophosphate

[0122] Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecaneManganese(II) Hexafluorophosphate

[0123] Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II) Chloride

[0124]Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecaneManganese(II) Chloride

[0125] Preferred complexes useful as transition-metal oxidationcatalysts more generally include not only monometallic, mononuclearkinds such as those illustrated hereinabove but also bimetallic,trimetallic or cluster kinds, especially when the polymetallic kindstransform chemically in the presence of a primary oxidant to form amononuclear, monometallic active species. Monometallic, mononuclearcomplexes are preferred. As defined herein, a monometallictransition-metal oxidation catalyst contains only one transition metalatom per mole of complex. A monometallic, mononuclear complex is one inwhich any donor atoms of the essential macrocyclic ligand are bonded tothe same transition metal atom, that is, the essential ligand does not“bridge” across two or more transition-metal atoms.

[0126] Transition Metals of the Catalyst

[0127] Just as the macropolycyclic ligand cannot vary indeterminatelyfor the present useful purposes, nor can the metal. An important part ofthe invention is to arrive at a match between ligand selection and metalselection which results in excellent oxidation catalysis. In general,transition-metal oxidation catalysts herein comprise a transition metalselected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III),V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II),Ru(III), and Ru(IV).

[0128] Preferred transition-metals in the instant transition-metaloxidation catalyst include manganese, iron and chromium. Preferredoxidation states include the (II) and (III) oxidation states.Manganese(II) in both the low-spin configuration and high spin complexesare included. It is to be noted that complexes such as low-spin Mn(II)complexes are rather rare in all of coordination chemistry. Thedesignation (II) or (III) denotes a coordinated transition metal havingthe requisite oxidation state; the coordinated metal atom is not a freeion or one having only water as a ligand.

[0129] Ligands

[0130] In general, as used herein, a “ligand” is any moiety capable ofdirect covalent bonding to a metal ion. Ligands can be charged orneutral and may range widely, including simple monovalent donors, suchas chloride, or simple amines which form a single coordinate bond and asingle point of attachment to a metal; to oxygen or ethylene, which canform a three-membered ring with a metal and thus can be said to have twopotential points of attachment, to larger moieties such asethylenediamine or aza macrocycles, which form up to the maximum numberof single bonds to one or more metals that are allowed by the availablesites on the metal and the number of lone pairs or alternate bondingsites of the free ligand. Numerous ligands can form bonds other thansimple donor bonds, and can have multiple points of attachment.

[0131] Ligands useful herein can fall into several groups: the essentialmacropolycyclic rigid ligand, preferably a cross-bridged macropolycycle(preferably there will be one such ligand in a useful transition-metalcomplex, but more, for example two, can be present, but not in preferredmononuclear complexes); other, optional ligands, which in general aredifferent from the essential cross-bridged macropolycycle (generallythere will be from 0 to 4, preferably from 1 to 3 such ligands); andligands associated transiently with the metal as part of the catalyticcycle, these latter typically being related to water, hydroxide, oxygen,water, hydroxide, or peroxides. Ligands of the third group are notessential for defining the metal oxidation catalyst, which is a stable,isolable chemical compound that can be fully characterized. Ligandswhich bind to metals through donor atoms each having at least a singlelone pair of electrons available for donation to a metal have a donorcapability, or potential denticity, at least equal to the number ofdonor atoms. In general, that donor capability may be fully or onlypartially exercised.

[0132] Macropolycyclic Rigid Ligands

[0133] To arrive at the instant transition-metal catalysts, amacropolycyclic rigid ligand is essential. This is coordinated(covalently connected to any of the above-identified transition-metals)by at least three, preferably at least four, and most preferably four orfive, donor atoms to the same transition metal.

[0134] Generally, the macropolycyclic rigid ligands herein can be viewedas the result of imposing additional structural rigidity on specificallyselected “parent macrocycles”. The term “rigid” herein has been definedas the constrained converse of flexibility: see D. H. Busch., ChemicalReviews., (1993), 93, 847-860, incorporated by reference. Moreparticularly, “rigid” as used herein means that the essential ligand, tobe suitable for the purposes of the invention, must be determinably morerigid than a macrocycle (“parent macrocycle”) which is otherwiseidentical (having the same ring size and type and number of atoms in themain ring) but lacks the superstructure (especially linking moieties or,preferably cross-bridging moieties) of the present ligands. Indetermining the comparative rigidity of the macrocycles with and withoutsuperstructures, the practitioner will use the free form (not themetal-bound form) of the macrocycles. Rigidity is well-known to beuseful in comparing macrocycles; suitable tools for determining,measuring or comparing rigidity include computational methods (see, forexample, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancocket al., Inorganica Chimica Acta, (1989), 164, 73-84. A determination ofwhether one macrocycle is more rigid than another can be often made bysimply making a molecular model, thus it is not in general essential toknow configurational energies in absolute terms or to precisely computethem. Excellent comparative determinations of rigidity of one macrocyclevs. another can be made using inexpensive personal computer-basedcomputational tools, such as ALCHEMY III, commercially available fromTripos Associates. Tripos also has available more expensive softwarepermitting not only comparative, but absolute determinations;alternately, SHAPES can be used (see Zimmer cited supra). Oneobservation which is significant in the context of the present inventionis that there is an optimum for the present purposes when the parentmacrocycle is distinctly flexible as compared to the cross-bridged form.Thus, unexpectedly, it is preferred to use parent macrocycles containingat least four donor atoms, such as cyclam derivatives, and tocross-bridge them, rather than to start with a more rigid parentmacrocycle. Another observation is that cross-bridged macrocycles aresignificantly preferred over macrocycles which are bridged in othermanners.

[0135] The macrocyclic rigid ligands herein are of course not limited tobeing synthesized from any preformed macrocycle plus preformed“rigidizing” or “conformation-modifying” element: rather, a wide varietyof synthetic means, such as template syntheses, are useful. See forexample Busch et al., reviewed in “Heterocyclic compounds: Aza-crownmacrocycles”, J. S. Bradshaw et. al., referred to in the BackgroundSection hereinbefore, for synthetic methods.

[0136] In one aspect of the present invention, the macropolycyclic rigidligands herein include those comprising:

[0137] (i) an organic macrocycle ring containing three, preferably four,or more donor atoms (preferably at least 3, more preferably at least 4,of these donor atoms are N) separated from each other by covalentlinkages of at least one, preferably 2 or 3, non-donor atoms, two tofive (preferably three to four, more preferably four) of these donoratoms being coordinated to the same transition metal in the complex; and

[0138] (ii) a linking moiety, preferably a cross-bridging chain, whichcovalently connects at least 2 (preferably non-adjacent) donor atoms ofthe organic macrocycle ring, said covalently connected (preferablynon-adjacent) donor atoms being bridgehead donor atoms which arecoordinated to the same transition metal in the complex, and whereinsaid linking moiety (preferably a cross-bridged chain) comprises from 2to about 10 atoms (preferably the cross-bridged chain is selected from2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donoratom).

[0139] While clear from the various contexts and illustrations alreadypresented, the practitioner may further benefit if certain terms receiveadditional definition and illustration. As used herein, “macrocyclicrings” are covalently connected rings formed from three or more,preferably four or more, donor atoms (i.e., heteroatoms such as nitrogenor oxygen) with carbon chains connecting them, and any macrocycle ringas defined herein must contain a total of at least ten, preferably atleast twelve, atoms in the macrocycle ring. A macropolycyclic rigidligand herein may contain more than one ring of any sort per ligand, butat least one macrocycle ring must be identifiable. Moreover, in thepreferred embodiments, no two hetero-atoms are directly connected.Preferred transition-metal oxidation catalysts are those wherein themacropolycyclic rigid ligand comprises an organic macrocycle ring (mainring) containing at least 10-20 atoms, preferably 12-18 atoms, morepreferably from about 12 to about 20 atoms, most preferably 12 to 16atoms.

[0140] “Donor atoms” herein are heteroatoms such as nitrogen, oxygen,phosphorus or sulfur, which when incorporated into a ligand still haveat least one lone pair of electrons available for forming adonor-acceptor bond with a metal. Preferred transition-metal oxidationcatalyst are those wherein the donor atoms in the organic macrocyclering of the cross-bridged macropolycyclic ligand are selected from thegroup consisting of N, O, S, and P, preferably N and O, and mostpreferably all N. Also preferred are cross-bridged macropolycyclicligands comprising 4 or 5 donor atoms, all of which are coordinated tothe same transition metal. Most preferred transition-metal oxidationcatalysts are those wherein the cross-bridged macropolycyclic ligandcomprises 4 nitrogen donor atoms all coordinated to the same transitionmetal, and those wherein the cross-bridged macropolycyclic ligandcomprises 5 nitrogen atoms all coordinated to the same transition metal.

[0141] “Non-donor atoms” of the macropolycyclic rigid ligand herein aremost commonly carbon, though a number of atom types can be included,especially in optional exocyclic substituents (such as “pendant”moieties, illustrated hereinafter) of the macrocycles, which are neitherdonor atoms for purposes essential to form the metal catalysts, nor arethey carbon. Thus, in the broadest sense, the term “non-donor atoms” canrefer to any atom not essential to forming donor bonds with the metal ofthe catalyst. Examples of such atoms could include heteroatoms such assulfur as incorporated in a non-coordinatable sulfonate group,phosphorus as incorporated into a phosphonium salt moiety, phosphorus asincorporated into a P(V) oxide, a non-transition metal, or the like. Incertain preferred embodiments, all non-donor atoms are carbon.

[0142] The term “macropolycyclic ligand” is used herein to refer to theessential ligand required for forming the essential metal catalyst. Asindicated by the term, such a ligand is both a macrocycle and ispolycyclic. “Polycyclic” means at least bicyclic in the conventionalsense. The essential macropolycyclic ligands must be rigid, andpreferred ligands must also cross-bridged.

[0143] Non-limiting examples of macropolycyclic rigid ligands, asdefined herein, include 1.3-1.7:

[0144] Ligand 1.3 is a macropolycylic rigid ligand in accordance withthe invention which is a highly preferred, cross-bridged,methyl-substituted (all nitrogen atoms tertiary) derivative of cyclam.Formally, this ligand is named5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using theextended von Baeyer system. See “A Guide to IUPAC Nomenclature ofOrganic Compounds: Recommendations 1993”, R. Panico, W. H. Powell andJ-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; seeespecially section R-2.4.2.1. According to conventional terminology, N1and N8 are “bridgehead atoms”; as defined herein, more particularly“bridgehead donor atoms” since they have lone pairs capable of donationto a metal. Ni is connected to two non-bridgehead donor atoms, N5 andN12, by distinct saturated carbon chains 2,3,4 and 14,13 and tobridgehead donor atom N8 by a “linking moiety” a,b which here is asaturated carbon chain of two carbon atoms. N8 is connected to twonon-bridgehead donor atoms, N5 and N12, by distinct chains 6,7 and9,10,11. Chain a,b is a “linking moiety” as defined herein, and is ofthe special, preferred type referred to as a “cross-bridging” moiety.The “macrocyclic ring” of the ligand supra, or “main ring” (IUPAC),includes all four donor atoms and chains 2,3,4; 6,7; 9,10,11 and 13,14but not a,b. This ligand is conventionally bicyclic. The short bridge or“linking moiety” a,b is a “cross-bridge” as defined herein, with a,bbisecting the macrocyclic ring.

[0145] Ligand 1.4 lies within the general definition of macropolycyclicrigid ligands as defined herein, but is not a preferred ligand since itis not “cross-bridged” as defined herein. Specifically, the “linkingmoiety” a,b connects “adjacent” donor atoms N1 and N12, which is outsidethe preferred embodiment of the present invention: see for comparisonthe preceding macrocyclic rigid ligand, in which the linking moiety a,bis a cross-bridging moiety and connects “non-adjacent” donor atoms.

[0146] Ligand 1.5 lies within the general definition of macropolycyclicrigid ligands as defined herein, but is not a preferred ligand since itcontains only three donor atoms, all of which are bridgehead donoratoms.

[0147] Ligand 1.6 lies within the general definition of macropolycylicrigid ligands as defined herein. This ligand can be viewed as a “mainring” which is a tetraazamacrocycle having three bridgehead donor atoms.This macrocycle is bridged by a “linking moiety” having a structure morecomplex than a simple chain, containing as it does a secondary ring. Thelinking moiety includes both a “cross-bridging” mode of bonding, and anon-cross-bridging mode.

[0148] Ligand 1.7 lies within the general definition of macropolycylicrigid ligands. Five donor atoms are present; two being bridgehead donoratoms. This ligand is a preferred cross-bridged ligand. It contains noexocyclic or pendant substituents which have aromatic content.

[0149] In contrast, for purposes of comparison, the following ligands(1.8 and 1.9) conform neither with the broad definition ofmacropolycyclic rigid ligands in the present invention, nor with thepreferred cross-bridged sub-family thereof and therefore are completelyoutside the present invention

[0150] In the ligand supra, neither nitrogen atom is a bridgehead donoratom. There are insufficient donor atoms.

[0151] The ligand supra is also outside the present invention. Thenitrogen atoms are not bridgehead donor atoms, and the two-carbonlinkage between the two main rings does not meet the inventiondefinition of a “linking moiety” since, instead of linking across asingle macrocycle ring, it links two different rings. The linkagetherefore does not confer rigidity as used in the term “macropolycyclicrigid ligand”. See the definition of “linking moiety” hereinafter.

[0152] Generally, the essential macropolycyclic rigid ligands (and thecorresponding transition-metal catalysts) herein comprise:

[0153] (a) at least one macrocycle main ring comprising three or moreheteroatoms; and

[0154] (b) a covalently connected non-metal superstructure capable ofincreasing the rigidity of the macrocycle, preferably selected from

[0155] (i) a bridging superstructure, such as a linking moiety;

[0156] (ii) a cross-bridging superstructure, such as a cross-bridginglinking moiety; and

[0157] (iii) combinations thereof.

[0158] The term “superstructure” is used herein as defined by Busch etal., in the Chemical Reviews article incorporated hereinabove.

[0159] Preferred superstructures herein not only enhance the rigidity ofthe parent macrocycle, but also favor folding of the macrocycle so thatit co-ordinates to a metal in a cleft. Suitable superstructures can beremarkably simple, for example a linking moiety such as any of thoseillustrated in 1.10 and 1.11 below, can be used.

[0160] wherein n is an integer, for example from 2 to 8, preferably lessthan 6, typically 2 to 4, or

[0161] wherein m and n are integers from about 1 to 8, more preferablyfrom 1 to 3; Z is N or CH; and T is a compatible substituent, forexample H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or thelike. The aromatic ring in 1.11 can be replaced by a saturated ring, inwhich the atom in Z connecting into the ring can contain N, O, S or C.

[0162] Without intending to be limited by theory, it is believed thatthe preorganization built into the macropolycyclic ligands herein thatleads to extra kinetic and/or thermodynamic stability of their metalcomplexes arises from either or both of topological constraints andenhanced rigidity (loss of flexibility) compared to the free parentmacrocycle which has no superstructure. The macropolycyclic rigidligands as defined herein and their preferred cross-bridged sub-family,which can be said to be “ultra-rigid”, combine two sources of fixedpreorganization. In preferred ligands herein, the linking moieties andparent macrocycle rings are combined to form ligands which have asignificant extent of “fold”, typically greater than in many knownsuperstructured ligands in which a superstructure is attached to alargely planar, often unsaturated macrocycle. See, for example, : D. H.Busch, Chemical Reviews, (1993), 93, 847-880. Further, the preferredligands herein have a number of particular properties, including (1)they are characterized by very high proton affinities, as in so-called“proton sponges”; (2) they tend to react slowly with multivalenttransition metals, which when combined with (1) above, renders synthesisof their complexes with certain hydrolyzable metal ions difficult inhydroxylic solvents; (3) when they are coordinated to transition metalatoms as identified herein, the ligands result in complexes that haveexceptional kinetic stability such that the metal ions only dissociateextremely slowly under conditions that would destroy complexes withordinary ligands; and (4) these complexes have exceptional thermodynamicstability; however, the unusual kinetics of ligand dissociation from thetransition metal may defeat conventional equilibrium measurements thatmight quantitate this property.

[0163] Other usable but more complex superstructures suitable for thepresent invention purposes include those containing an additional ring,such as in 1.6. Other bridging superstructures when added to amacrocycle include, for example, 1.4. In contrast, cross-bridgingsuperstructures unexpectedly produce a substantial improvement in theutility of a macrocyclic ligand for use in oxidation catalysis: apreferred cross-bridging superstructure is 1.3. A superstructureillustrative of a bridging plus cross-bridging combination is 1.12:

[0164] In 1.12, linking moiety (i) is cross-bridging, while linkingmoiety (ii) is not. 1.12 is less preferred than 1.3.

[0165] More generally, a “linking moiety”, as defined herein, is acovalently linked moiety comprising a plurality of atoms which has atleast two points of covalent attachment to a macrocycle ring and whichdoes not form part of the main ring or rings of the parent macrocycle.In other terms, with the exception of the bonds formed by attaching itto the parent macrocycle, a linking moiety is wholly in asuperstructure.

[0166] The terms “cross-bridged” or “cross-bridging”, as used herein,refers to covalent ligation, bisection or “tying” of a macrocycle ringin which two donor atoms of the macrocycle ring are covalently connectedby a linking moiety, for example an additional chain distinct from themacrocycle ring, and further, preferably, in which there is at least onedonor atom of the macrocycle ring in each of the sections of themacrocycle ring separated by the ligation, bisection or tying.Cross-bridging is not present in structure 1.4 hereinabove; it ispresent in 1.3, where two donor atoms of a preferred macrocycle ring areconnected in such manner that there is not a donor atom in each of thebisection rings. Of course, provided that cross-bridging is present, anyother kind of bridging can optionally be added and the bridgedmacrocycle will retain the preferred property of being “cross-bridged”:see Structure 1.12. A “cross-bridged chain” or “cross-bridging chain”,as defined herein, is thus a highly preferred type of linking moietycomprising a plurality of atoms which has at least two points ofcovalent attachment to a macrocycle ring and which does not form part ofthe original macrocycle ring (main ring), and further, which isconnected to the main ring using the rule identified in defining theterm “cross-bridging”.

[0167] The term “adjacent” as used herein in connection with donor atomsin a macrocycle ring means that there are no donor atoms interveningbetween a first donor atom and another donor atom within the macrocyclering; all intervening atoms in the ring are non-donor atoms, typicallythey are carbon atoms. The complementary term “non-adjacent” as usedherein in connection with donor atoms in a macrocycle ring means thatthere is at least one donor atom intervening between a first donor atomand another that is being referred to. In preferred cases such as across-bridged tetraazamacrocycle, there will be at least a pair ofnon-adjacent donor atoms which are bridgehead atoms, and a further pairof non-bridgehead donor atoms.

[0168] “Bridgehead” atoms herein are atoms of a macropolycyclic ligandwhich are connected into the structure of the macrocycle in such mannerthat each non-donor bond to such an atom is a covalent single bond andthere are sufficient covalent single bonds to connect the atom termed“bridgehead” such that it forms a junction of at least two rings, thisnumber being the maximum observable by visual inspection in theuncoordinated ligand.

[0169] In general, the metal oxidation catalysts herein may containbridgehead atoms which are carbon, however, and importantly, in certainpreferred embodiments, all essential bridgehead atoms are heteroatoms,all heteroatoms are tertiary, and further, they each co-ordinate throughlone pair donation to the metal. Thus, bridgehead atoms are junctionpoints not only of rings in the macrocycle, but also of chelate rings.

[0170] The term “a further donor atom” unless otherwise specificallyindicated, as used herein, refers to a donor atom other than a donoratom contained in the macrocycle ring of an essential macropolycycle.For example, a “further donor atom” may be present in an optionalexocyclic substituent of a macrocyclic ligand , or in a cross-bridgedchain thereof. In certain preferred embodiments, a “further donor atom”is present only in a cross-bridged chain.

[0171] The term “coordinated with the same transition metal” as usedherein is used to emphasize that a particular donor atom or ligand doesnot bind to two or more distinct metal atoms, but rather, to only one.

[0172] Optional Ligands

[0173] It is to be recognized for the transition-metal oxidationcatalysts useful in the present invention catalytic systems thatadditional non-macropolycyclic ligands may optionally also becoordinated to the metal, as necessary to complete the coordinationnumber of the metal complexed. Such ligands may have any number of atomscapable of donating electrons to the catalyst complex, but preferredoptional ligands have a denticity of 1 to 3, preferably 1. Examples ofsuch ligands are H₂O, ROH, NR₃, RCN, OH⁻, OOH⁻, RS⁻, RO⁻, RCOO⁻, OCN⁻,SCN⁻, N₃ ⁻, CN⁻, F⁻, Cl⁻, Br⁻, I⁻, O²⁻, NO³⁻, NO²⁻, SO₄ ²⁻, SO₃ ², PO₄³⁻, organic phosphates, organic phosphonates, organic sulfates, organicsulfonates, and aromatic N donors such as pyridines, pyrazines,pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles andthiazoles with R being H, optionally substituted alkyl, optionallysubstituted aryl. Preferred transition-metal oxidation catalystscomprise one or two non-macropolycyclic ligands.

[0174] The term “non-macropolycyclic ligands” is used herein to refer toligands such as those illustrated immediately hereinabove which ingeneral are not essential for forming the metal catalyst, and are notcross-bridged macropolycycles. “Not essential”, with reference to suchnon-macropolycyclic ligands means that, in the invention as broadlydefined, they can be substituted by a variety of common alternateligands. In highly preferred embodiments in which metal, macropolycyclicand non-macropolycyclic ligands are finely tuned into a transition-metaloxidation catalyst, there may of course be significant differences inperformance when the indicated non-macropolycyclic ligand(s) arereplaced by further, especially non-illustrated, alternative ligands.

[0175] The term “metal catalyst” or “transition-metal oxidationcatalyst” is used herein to refer to the essential catalyst compound ofthe invention and is commonly used with the “metal” qualifier unlessabsolutely clear from the context. Note that there is a disclosurehereinafter pertaining specifically to optional catalyst materials.Therein the term “bleach catalyst” may be used unqualified to refer tooptional, organic (metal-free) catalyst materials, or to optionalmetal-containing catalysts that lack the advantages of the essentialcatalyst: such optional materials, for example, include known metalporphyrins or metal-containing photobleaches. Other optional catalyticmaterials herein include enzymes.

[0176] The macropolycyclic rigid ligands of the inventive compositionsand methods also include ligands selected from the group consisting of:

[0177] (i) the macropolycyclic rigid ligand of formula (I) havingdenticity of 3 or, preferably, 4:

[0178] (ii) the macropolycyclic rigid ligand of formula (II) havingdenticity of 4 or 5:

[0179] (iii) the macropolycyclic rigid ligand of formula (II) havingdenticity of 5 or 6:

[0180] (iv) the macropolycyclic rigid ligand of formula (IV) havingdenticity of 6 or 7:

[0181] wherein in these formulas:

[0182] each “E” is the moiety (CR_(n))_(a)−X—(CR_(n))_(a′), wherein X isselected from the group consisting of O, S, NR and P, or a covalentbond, and preferably X is a covalent bond and for each E the sum of a+a′is independently selected from 1 to 5, more preferably 2 and 3;

[0183] each “G” is the moiety (CR_(n))_(b);

[0184] each “R” is independently selected from H, alkyl, alkenyl,alkynyl, aryl, alkylaryl (e.g., benzyl), and heteroaryl, or two or moreR are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,or heterocycloalkyl ring;

[0185] each “D” is a donor atom independently selected from the groupconsisting of N, O, S, and P, and at least two D atoms are bridgeheaddonor atoms coordinated to the transition metal;

[0186] “B” is a carbon atom or “D” donor atom, or a cycloalkyl orheterocyclic ring;

[0187] each “n” is an integer independently selected from 1 and 2,completing the valence of the carbon atoms to which the R moieties arecovalently bonded;

[0188] each “n′” is an integer independently selected from 0 and 1,completing the valence of the D donor atoms to which the R moieties arecovalently bonded;

[0189] each “n″” is an integer independently selected from 0, 1, and 2completing the valence of the B atoms to which the R moieties arecovalently bonded;

[0190] each “a” and “a′” is an integer independently selected from 0-5,preferably a+a′ equals 2 or 3, wherein the sum of all “a” plus “a′” inthe ligand of formula (I) is within the range of from about 7 to about12, the sum of all “a” plus “a′” in the ligand of formula (II) is withinthe range of from about 6 (preferably 8) to about 12, the sum of all “a”plus “a′” in the ligand of formula (III) is within the range of fromabout 8 (preferably 10) to about 15, and the sum of all “a” plus “a′” inthe ligand of formula (IV) is within the range of from about 10(preferably 12) to about 18;

[0191] each “b” is an integer independently selected from 0-5, or in anyof the above formulas, one or more of the (CR_(n))_(b) moietiescovalently bonded from any D to the B atom is absent as long as at leasttwo (CR_(n))_(b) covalently bond two of the D donor atoms to the B atomin the formula, and the sum of all “b” is within the range of from about1 to about 5. Preferred ligands of the above formulas are those whichare cross-bridged macropolycyclic ligands having Formulas (II), (III) or(IV).

[0192] It is to be noted herein that for the above formulas wherein “a′”or “a′” is 1, these ligands are not preferred for potential instabilityreasons in selected solvents, but are still within the scope of thepresent invention.

[0193] Preferred are the transition-metal oxidation catalysts wherein inthe cross-bridged macropolycyclic ligand the D and B are selected fromthe group consisting of N and O, and preferably all D are N. Alsopreferred are wherein in the cross-bridged macropolycyclic ligand all“a” are independently selected from the integers 2 and 3, all X areselected from covalent bonds, all “a′” are 0, and all “b” areindependently selected from the integers 0, 1, and 2. Tetradentate andpentadentate cross-bridged macropolycyclic ligands are most preferred.

[0194] Unless otherwise specified, the convention herein when referringto denticity, as in “the macropolycycle has a denticity of four” will beto refer to a characteristic of the ligand: namely, the maximum numberof donor bonds that it is capable of forming when it coordinates to ametal. Such a ligand is identified as “tetradentate”. Similarly, amacropolycycle containing five nitrogen atoms each with a lone pair isreferred to as “pentadentate”. The present invention encompassescatalytic systems in which the macrocyclic rigid ligand exerts its fulldenticity, as stated, in the transition-metal catalyst complexes;moreover, the invention also encompasses any equivalents which can beformed, for example, if one or more donor sites are not directlycoordinated to the metal. This can happen, for example, when apentadentate ligand coordinates through four donor atoms to thetransition metal and one donor atom is protonated.

[0195] The further to illustrate preferred catalytic systems, theinvention also includes those containing metal catalysts wherein thecross-bridged macropolycyclic ligand is a bicyclic ligand; preferablythe cross-bridged macropolycyclic ligand is a macropolycyclic moiety offormula (II) having the formula:

[0196] wherein each “a” is independently selected from the integers 2 or3, and each “b” is independently selected from the integers 0, 1 and 2.

[0197] Further preferred are the compositions containing cross-bridgedmacropoly-cyclic ligands having the formula:

[0198] wherein in this formula:

[0199] each “n” is an integer independently selected from 1 and 2,completing the valence of the carbon atom to which the R moieties arecovalently bonded;

[0200] each “R” and “R¹” is independently selected from H, alkyl,alkenyl, alkynyl, aryl, alkylaryl (e.g., benzyl) and heteroaryl, or Rand/or R¹ are covalently bonded to form an aromatic, heteroaromatic,cycloalkyl, or heterocycloalkyl ring, and wherein preferably all R are Hand R¹ are independently selected from linear or branched, substitutedor unsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;

[0201] each “a” is an integer independently selected from 2 or 3;

[0202] preferably all nitrogen atoms in the cross-bridged macropolycyclerings are coordinated with the transition metal.

[0203] The invention further includes the novel methods, compositions,and transition-metal catalysts which include the transition-metalcomplexes, preferably the Mn, Fe and Cr complexes, or preferredcross-bridged macropolycyclic ligands having the formula:

[0204] wherein in this formula “R¹” is independently selected from H,and linear or branched, substituted or unsubstituted C₁-C₂₀ alkyl,alkylaryl, alkenyl or alkynyl, more preferably R¹ is alkyl or alkylaryl;and preferably all nitrogen atoms in the macropolycyclic rings arecoordinated with the transition metal.

[0205] Also preferred are cross-bridged macropolycyclic ligands havingthe formula:

[0206] wherein in this formula:

[0207] each “n” is an integer independently selected from 1 and 2,completing the valence of the carbon atom to which the R moieties arecovalently bonded;

[0208] each “R” and “R¹” is independently selected from H, alkyl,alkenyl, alkynyl, aryl, alkylaryl (e.g., benzyl), and heteroaryl, or Rand/or R¹ are covalently bonded to form an aromatic, heteroaromatic,cycloalkyl, or heterocycloalkyl ring, and wherein preferably all R are Hand R¹ are independently selected from linear or branched, substitutedor unsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;

[0209] each “a” is an integer independently selected from 2 or 3;

[0210] preferably all nitrogen atoms in the macropolycyclic rings arecoordinated with the transition metal. In terms of the presentinvention, even though any of such ligands are known, the inventionencompasses the use of these ligands in the form of theirtransition-metal complexes as oxidation catalysts, or in the form of thedefined catalytic systems.

[0211] In like manner, included in the definition of the preferredcross-bridged macropolycyclic ligands are those having the formula:

[0212] wherein in either of these formulae, “R¹” is independentlyselected from H, or, preferably, linear or branched, substituted orunsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl; and preferably allnitrogen atoms in the macropolycyclic rings are coordinated with thetransition metal.

[0213] The present invention has numerous variations and alternateembodiments which do not depart from its spirit and scope. Thus, in theforegoing catalytic systems, the macropolycyclic ligand can be replacedby any of the following:

[0214] In the above, the R, R′, R″, R′″ moieties can, for example, bemethyl, ethyl or propyl. (Note that in the above formalism, the shortstraight strokes attached to certain N atoms are an alternaterepresentation for a methyl group).

[0215] While the above illustrative structures involve tetra-azaderivatives (four donor nitrogen atoms), ligands and the correspondingcomplexes in accordance with the present invention can also be made, forexample from any of the following:

[0216] Moreover, using only a single organic macropolycycle, preferablya cross-bridged derivative of cyclam, a wide range of oxidation catalystcompounds of the invention may be prepared; numerous of these arebelieved to be novel chemical compounds. Preferred transition-metalcatalysts of both cyclam-derived and non-cyclam-derived cross-bridgedkinds are illustrated, but not limited, by the following:

[0217] In other embodiments of the invention, transition-metalcomplexes, such as the Mn, Fe or Cr complexes, especially (II) and/or(III) oxidation state complexes, of the hereinabove-identified metalswith any of the following ligands are also included:

[0218] wherein R¹ is independently selected from H (preferably non-H)and linear or branched, substituted or unsubstituted C₁-C₂₀ alkyl,alkenyl or alkynyl and L is any of the linking moieties given herein,for example 1.10 or 1.11;

[0219] wherein R¹ is as defined supra; m,n,o and p can varyindependently and are integers which can be zero or a positive integerand can vary independently while respecting the provision that the summ+n+o+p is from 0 to 8 and L is any of the linking moieties definedherein;

[0220] wherein X and Y can be any of the R¹ defined supra, m,n,o and pare as defined supra and q is an integer, preferably from 1 to 4; or,more generally,

[0221] wherein L is any of the linking moieties herein, X and Y can beany of the R¹ defined supra, and m,n,o and p are as defined supra.Alternately, another useful ligand is:

[0222] wherein R¹ is any of the R¹ moieties defined supra.

[0223] Pendant Moieties

[0224] Macropolycyclic rigid ligands and the correspondingtransition-metal complexes and oxidation catalytic systems herein mayalso incorporate one or more pendant moieties, in addition to, or as areplacement for, R¹ moieties. Such pendant moieties are nonlimitinglyillustrated by any of the following:

[0225] wherein R is, for example, a C₁-C₁₂ alkyl, more typically a C₁-C₄alkyl, and Z and T are as defined in 1.11. Pendant moieties may beuseful, for example, if it is desired to adjust the solubility of thecatalyst in a particular solvent adjunct.

[0226] Alternately, complexes of any of the foregoing highly rigid,cross-bridged macropolycyclic ligands with any of the metals indicatedare equally within the invention.

[0227] Preferred are catalysts wherein the transition metal is selectedfrom manganese and iron, and most preferably manganese. Also preferredare catalysts wherein the molar ratio of transition metal tomacropolycyclic ligand in the oxidation catalyst is 1:1, and morepreferably wherein the catalyst comprises only one metal per oxidationcatalyst complex. Further preferred transition-metal oxidation catalystsare monometallic, mononuclear complexes. The term “monometallic,mononuclear complex” is used herein in referring to an essentialtransition-metal oxidation catalyst compound to identify and distinguisha preferred class of compounds containing only one metal atom per moleof compound and only one metal atom per mole of cross-bridgedmacropolycyclic ligand.

[0228] Preferred transition-metal oxidation catalysts also include thosewherein at least four of the donor atoms in the macropolycyclic rigidligand, preferably at least four nitrogen donor atoms, two of which forman apical bond angle with the same transition metal of 180±50° and twoof which form at least one equatorial bond angle of 90±20°. Suchcatalysts preferably have four or five nitrogen donor atoms in total andalso have coordination geometry selected from distorted octahedral(including trigonal antiprismatic and general tetragonal distortion) anddistorted trigonal prismatic, and preferably wherein further thecross-bridged macropolycyclic ligand is in the folded conformation (asdescribed, for example, in Hancock and Martell, Chem. Rev., 1989, 89, atpage 1894). A folded conformation of a cross-bridged macropolycyclicligand in a transition-metal complex is further illustrated below:

[0229] This catalyst is the complex of Example 1 hereinafter. The centeratom is Mn; the two ligands to the right are chloride; and a Bcyclamligand occupies the left side of the distorted octahedral structure. Thecomplex contains an angle N—Mn—N of 158° incorporating the two mutuallytrans-donor atoms in “axial” positions; the corresponding angle N—Mn—Nfor the nitrogen donor atoms in plane with the two chloride ligands is83.2 Stated alternately, the preferred synthetic, laundry, cleaning,papermaking, or effluent-treating catalytic systems herein containtransition-metal complexes of a macropolycyclic ligand in which there isa major energetic preference of the ligand for a folded, as distinctfrom an “open” and/or “planar” and or “flat” conformation. Forcomparison, a disfavored conformation is, for example, either of thetrans-structures shown in Hancock and Martell, Chemical Reviews, (1989),89 at page 1894 (see FIG. 18), incorporated by reference.

[0230] In light of the foregoing coordination description, the presentinvention includes oxidation catalytic systems comprising atransition-metal oxidation catalyst, especially based on Mn(II) orMn(III) or correspondingly, Fe(II) or Fe(III) or Cr(II) or Cr(III),wherein two of the donor atoms in the macropolycyclic rigid ligand,preferably two nitrogen donor atoms, occupy mutually trans-positions ofthe coordination geometry, and at least two of the donor atoms in themacropolycyclic rigid ligand, preferably at least two nitrogen donoratoms, occupy cis-equatorial positions of the coordination geometry,including particularly the cases in which there is substantialdistortion as illustrated hereinabove.

[0231] The present catalytic systems can, furthermore, includetransition metal oxidation catalysts in which the number of asymmetricsites can vary widely; thus both S- and R-absolute conformations can beincluded for any stereochemically active site. Other types of isomerism,such as geometric isomerism, are also included. The transition-metaloxidation catalyst can further include mixtures of geometric orstereoisomers.

[0232] Purification of Catalyst

[0233] In general, the state of purity of the transition-metal oxidationcatalyst can vary, provided that any impurities, such as byproducts ofthe synthesis, free ligand(s), unreacted transition-metal saltprecursors, colloidal organic or inorganic particles, and the like, arenot present in amounts which substantially decrease the utility of thetransition-metal oxidation catalyst. It has been discovered thatpreferred embodiments of the present invention include those in whichthe transition-metal oxidation catalyst is purified by any suitablemeans, such that it does not excessively consume available oxygen (AvO).Excessive AvO consumption is defined as including any instance ofexponential decrease in AvO levels of bleaching, oxidizing or catalyzingsolutions with time at 20-40 deg. C. Preferred transition-metaloxidation catalysts herein, whether purified or not, when placed intodilute aqueous buffered alkaline solution at a pH of about 9(carbonate/bicarbonate buffer) at temperatures of about 40 deg. C., havea relatively steady decrease in AvO levels with time; in preferredcases, this rate of decrease is linear or approximately linear. In thepreferred embodiments, there is a rate of AvO consumption at 40 deg Cgiven by a slope of a graph of %AvO vs. time (in sec.) (hereinafter “AvOslope”) of from about −0.0050 to about −0.0500, more preferably −0.0100to about −0.0200. Thus, a preferred Mn(II) oxidation catalyst inaccordance with the invention has an AvO slope of from about −0.0140 toabout −0.0182; in contrast, a somewhat less preferred transition metaloxidation catalyst has an AvO slope of −0.0286.

[0234] Preferred methods for determining AvO consumption in aqueoussolutions of transition metal oxidation catalysts herein include thewell-known iodometric method or its variants, such as methods commonlyapplied for hydrogen peroxide. See, for example, Organic Peroxides, Vol.2., D. Swem Ed.,), Wiley-Interscience, New York, 1971, for example thetable at p. 585 and references therein including P. D. Bartlett and R.Altscul, J. Amer. Chem. Soc., 67, 812 (1945) and W. E. Cass, J. Amer.Chem. Soc., 68, 1976 (1946). Accelerators such as ammonium molybdate canbe used. The general procedure used herein is to prepare an aqueoussolution of catalyst and hydrogen peroxide in a mild alkaline buffer,for example carbonate/bicarbonate at pH 9, and to monitor theconsumption of hydrogen peroxide by periodic removal of aliquots of thesolution which are “stopped” from further loss of hydrogen peroxide byacidification using glacial acetic acid, preferably with chilling (ice).These aliquots can then be analyzed by reaction with potassium iodide,optionally but sometimes preferably using ammonium molybdate (especiallylow-impurity molybdate, see for example U.S. Pat. No. 4,596,701) toaccelerate complete reaction, followed by back-titratation using sodiumthiosulfate. Other variations of analytical procedure can be used, suchas thermometric procedures, potential buffer methods (Ishibashi et al.,Anal. Chim. Acta (1992), 261(1-2), 405-10) or photometric procedures fordetermination of hydrogen peroxide (EP 485,000 A2, May 13, 1992).Variations of methods permitting fractional determinations, for exampleof peracetic acid and hydrogen peroxide, in presence or absence of theinstant transition-metal oxidation catalysts are also useful; see, forexample JP 92-303215, Oct. 16, 1992.

[0235] In another embodiment of the present invention, there areencompassed laundry and cleaning compositions incorporatingtransition-metal oxidation catalysts which have been purified to theextent of having a differential AvO loss reduction , relative to theuntreated catalyst, of at least about 10% (units here are dimensionlesssince they represent the ratio of the AvO slope of the treatedtransition-metal oxidation catalyst over the AvO slope for the untreatedtransition metal oxidation catalyst—effectively a ratio of AvO's). Inother terms, the AvO slope is improved by purification so as to bring itinto the above-identified preferred ranges.

[0236] In yet another embodiment of the instant invention, two processeshave been identified which are particularly effective in improving thesuitability of transition-metal oxidation catalysts, as synthesized, forincorporation into laundry and cleaning products or for other usefuloxidation catalysis applications. One such process is any process havinga step of treating the transition-metal oxidation catalyst, as prepared,by extracting the transition-metal oxidation catalyst, in solid form,with an aromatic hydrocarbon solvent; suitable solvents areoxidation-stable under conditions of use and include benzene andtoluene, preferably toluene. Surprisingly, toluene extraction canmeasurably improve the AvO slope (see disclosure hereinabove).

[0237] Another process which can be used to improve the AvO slope of thetransition metal oxidation catalyst is to filter a solution thereofusing any suitable filtration means for removing small or colloidalparticles. Such means include the use of fine-pore filters;centrifugation; or coagulation of the colloidal solids.

[0238] In more detail, a full procedure for purifying a transition-metaloxidation catalyst herein can include:

[0239] (a) dissolving the transition-metal oxidation catalyst, asprepared, in hot acetonitrile:

[0240] (b) filtering the resulting solution hot, e.g., at about 70 deg.C, through glass microfibers (for example glass microfiber filter paperavailable from Whatman);

[0241] (c) if desired, filtering the solution of the first filtrationthrough a 0.2 micron membrane (for example, a 0.2 micron filtercommercially available from Millipore) or centrifuging whereby colloidalparticles are removed;

[0242] (d) evaporating the solution of the second filtration to dryness;

[0243] (e) washing the solids of step (d) with toluene, for example fivetimes using toluene in an amount which is double the volume of theoxidation catalyst solids;

[0244] (f) drying the product of step (e).

[0245] Another procedure which can be used, in any convenientcombination with aromatic solvent washes and/or removal of fineparticles is recrystallization. Recrystallization, for example of Mn(II)Bcyclam chloride transition-metal oxidation catalyst, can be done fromhot acetonitrile. Recrystallization can have its disadvantages, forexample it may on occasion be more costly.

[0246] Catalytic Systems and Methods for Synthetic Oxidation Reactions

[0247] Methods and catalytic systems for oxidizing alkenes to epoxidesby treating the alkene with a transition-metal complex are known, forexample from U.S. Pat. Nos. 5,428,180 and 5,077,394. Epoxidations ofolefins can also be carried out according to the method of Collman, J.P.; Kodadek, T. J.; Raybuck, S. A.; and Meunier, B., Proc. Natl. Acad.Sci. U.S.A (1983), 80, 7039, and which publication is incorporatedherein by reference in its entirety. In the present invention, catalyticsystems and methods require the presence of the transition-metaloxidation catalysts described herein to effect such oxidative processes.

[0248] The catalytic systems for use herein suitably comprise atransition-metal oxidation catalyst as described herein, a primaryoxidation agent or primary oxidant, for example monopersulfate orperacetic acid or their salts, and a solvent. A wide range of protic andaprotic solvents can be used, covering a range of dielectric constants.The catalytic systems include solutions comprising at least about0.00001%, more preferably at least about 0.0001% of transition-metalcatalyst, from about 0.0001% to about 10%, by weight of primaryoxidation agent, and at least about 5%, more typically at least about50% of solvent. The amount of substrate (the compound to be oxidized)can vary in a wide range, in terms of proportion by weight to thecatalytic system. A suitable range of composition is from 1:10,000 toabout 10,000:1 of catalytic system to substrate by weight, moretypically from about 1:1,000 to about 1:1.

[0249] Similarly, other oxidation reactions for synthetic chemicalmanufacturing processes such as oxidation of sulfides to sulfones arecarried out according to the present invention utilizing catalyticsystems containing oxidation agent, transition-metal catalysts, andproportions of the materials as described herein. Again, it is preferredthat such processes use catalytic systems which are solutions of theseagents.

[0250] Catalytic Systems and Methods for Pulp Oxidation

[0251] The application of oxidizing agents in a sequence of delignifyingand bleaching treatment stages of unbleached chemical paper pulpprocesses are known, for example U.S. Pat. No. 5,431,781. The presentinvention catalytic systems and methods further require the presence ofthe transition-metal oxidation catalysts described herein to effect suchoxidative processes.

[0252] All types of wood used for the production of chemical pulps aresuitable for use in the process of the present invention. In particular,this includes those used for kraft pulps, namely the coniferous woodssuch as, for example, the species of pines and firs and the deciduouswoods such as, for example, yellow pine, beech, oak, eucalyptus andhornbeam.

[0253] Catalytic systems useful in pulp and paper treatment can, ingeneral, have a range of composition similar to that described supra fororganic synthetic purposes. The substrate in this instance is paper orpaper-derived materials having an oxidizable component, such as lignin.

[0254] In more detail, transition-metal catalysts herein can be usefulin a somewhat similar manner to the substituted porphyrin metalcomplexes of Dolphin (U.S. Pat. No. 5,077,394), though there can beadditional advantages, for example improved flexibility in the controlof water-solubility of catalyst as compared with certain porphyrinsystems. Thus transition-metal complexes identified herein may be usedin the form of catalyst systems including (a) the transition-metalcatalyst, (b) primary oxidant, for example peracetate, persulfate orperoxide, and (c) solvent such as water though nonaqueous, especiallypolar aprotic solvents such as dimethylformamide, acetonitrile,dimethylsulfoxide, alcohols e.g., methanol, ethanol, chlorinatedsolvents such as dichloromethane, chloroform or the like or combinationsof water and such organic solvents having a wide range in dielectricconstant may be used, together providing catalytic systems for oxidationapplicable to a variety of processes, for example those in which priorart optionally substituted phenyl porphyrins have been indicated asuseful. The transition-metal catalysts which are the more water solubleare particularly useful in those processes in which water solubility isdesired or required. Such processes include, by way of illustration, theoxidation of alkanes (including cycloalkanes), the oxidation of alkenes(including cycloalkenes), the oxidative conversion of lignin modelcompounds which are converted by the lignin modifying and degradingfungal enzymes also known as ligninases, the use in the modification ordegradation of lignin, and the use in the treating of wood in variousforms such as wood chips or pulp to assist in or effect pulping orbleaching.

[0255] Particular pulping-related processes of interest for the use ofthe water soluble transition-metal complexes, for example the Mn(II)Bcyclam complexes, for assisting in or effecting a modification ordegradation of lignin, include processes of making and oxidativelytreating the well-known mechanical pulps such as thermomechanical pulpsand kraft pulps so as to effect bleaching.

[0256] The invention also provides transition-metal complexes havingreduced water-solubility, such as those in which the macrocycle ligandcarries one or more long-chain alkyl pendant substituents, and these mayalso be used in various commercial applications such as solvent pulping,for example the known organosolv pulping process. Other uses include thedecomposition of organic contaminants in waste streams such as thechlorinated organic compounds in E1 effluent from the kraft pulpchlorine bleaching process.

[0257] Of particular interest is the use of the present transition-metalcatalysts, including the Fe, Mn (preferred for environmental reasons)and even Ni types as catalysts in the catalytic oxidation of alkanes(including cycloalkanes) for the hydroxylation of the same (or ultimateketo formation) and in the catalytic oxidation of alkenes (includingcycloalkenes) to form epoxides (epoxidation). Such hydroxylations andepoxidation are well-known reactions which are commonly carried out inan organic solvent which is redox-inert under the operating conditions,but water containing systems may also be used; hence both the watersoluble and water insoluble transition-metal complexes may be used insuch processes.

[0258] In general, the present transition-metal oxidant catalyticsystems may be used over a wide range of reaction temperatures includinghigh temperatures up to 150 deg. C. or even higher, and over a widerange of pH's which may extend from about 1 to 14, more suitably from pH2 to pH 12; nonetheless, it is particularly desirable to use thecatalysts at ambient or near-ambient temperatures where energy economyis desired, and to use mild pH's, which are desirably safe for materialhandling. The present catalyst systems have the advantage of beinguseful under such conditions.

[0259] The present invention includes use of the identifiedtransition-metal oxidation catalyst systems in the oxidativedelignification of wood-pulp. U.S. Pat. No. 5,552,019, for example,describes such delignification using polyoxometallates. The presentcatalyst systems, typically comprising (a) the transition-metalcatalyst; (b) a primary oxidant such as sodium hypochlorite or, morepreferably, potassium monopersulfate triple salt, the latter soldcommercially as OXONE by Du Pont and (c) pH-adjusting adjuncts can beused, especially at pH in the range from about 7.5 to about 9.5, undermild temperature conditions for delignification purposes.

[0260] The present invention has numerous alternate embodiments andramifications. For example, in the laundry detergents and laundrydetergent additives field, the invention includes all manner ofbleach-containing or bleach additive compositions, including forexample, fully-formulated heavy-duty granular detergents containingsodium perborate or sodium percarbonate and/or a preformed peracidderivative such as OXONE as primary oxidant, the transition-metalcatalyst of the invention, a bleach activator such astetraacetylethylenediamine or a similar compound, with or withoutnonanoyloxybenzenesulfonate sodium salt, and the like.

[0261] Other suitable composition forms include laundry bleach additivepowders, granular or tablet-form automatic dishwashing detergents,scouring powders and bathroom cleaners. In the solid-form compositions,the catalytic system may lack solvent (water)—this is added by the useralong with the substrate (a soiled surface) which is to be cleaned (orcontains soil to be oxidized).

[0262] Other desirable embodiments of the instant invention includedentifrice or denture cleaning compositions. Suitable compositions towhich the transition-metal complexes herein can be added include thedentifrice compositions containing stabilized sodium percarbonate, seefor example U.S. Pat. No. 5,424,060 and the denture cleaners of U.S.Pat. No. 5,476,607 which are derived from a mixture containing apregranulated compressed mixture of anhydrous perborate, perboratemonohydrate and lubricant, monopersulfate, non-granulated perboratemonohydrate, proteolytic enzyme and sequestering agent, thoughenzyme-free compositions are also very effective. Optionally,excipients, builders, colors, flavors, and surfactants can be added tosuch compositions, these being adjuncts characteristic of the intendeduse. RE32,771 describes another denture cleaning composition to whichthe instant transition-metal catalysts may profitably be added. Thus, bysimple admixture of, for example, about 0.00001% to about 0.1% of thepresent transition-metal catalyst, a cleaning composition is securedthat is particularly suited for compaction into tablet form; thiscomposition also comprises a phosphate salt, an improved perborate saltmixture wherein the improvement comprises a combination of anhydrousperborate and monohydrate perborate in the amount of about 50% to about70% by weight of the total cleansing composition, wherein thecombination includes at least 20% by weight of the total cleansingcomposition of anhydrous perborate, said combination having a portionpresent in a compacted granulated mixture with from about 0.01% to about0.70% by weight of said combination of a polymeric fluorocarbon, and achelating or sequestering agent present in amounts greater than about10% by weight up to about 50% by weight of the total composition, saidcleansing composition being capable of cleansing stained surfaces andthe like with a soaking time of five minutes or less when dissolved inaqueous solution and producing a marked improvement in clarity ofsolution upon disintegration and cleaning efficacy over the prior art.Of course, the denture cleaning composition need not extend to thesophistication of such compositions: adjuncts not essential to theprovision of catalytic oxidation such as the fluorinated polymer can beomitted if desired.

[0263] In another non-limiting illustration, the presenttransition-metal catalyst can be added to an effervescentdenture-cleaning composition comprising monoperphthalate, for examplethe magnesium salt thereof, and/or to the composition of U.S. Pat. No.4,490,269 incorporated herein by reference. Preferred denture cleansingcompositions include those having tablet form, wherein the tabletcomposition is characterized by active oxygen levels in the range fromabout 100 to about 200 mg/tablet; and compositions characterized byfragrance retention levels greater than about 50% throughout a period ofsix hours or greater. See U.S. Pat. No. 5,486,304 incorporated byreference for more detail in connection especially with fragranceretention.

[0264] The advantages and benefits of the instant invention includecleaning compositions which have superior bleaching compared tocompositions not having the selected transition-metal oxidationcatalyst. The superiority in bleaching is obtained using very low levelsof transition-metal oxidation catalyst. The invention includesembodiments which are especially suited for fabric washing, having a lowtendency to damage fabrics in repeated washings. However, numerous otherbenefits can be secured; for example, compositions an be relatively moreaggressive, as needed, for example, in tough cleaning of durable hardsurfaces, such as the interiors of ovens, or kitchen surfaces havingdifficult-to-remove films of soil. The compositions can be used both in“pre-treat” modes, for example to loosen dirt in kitchens or bathrooms;or in a “mainwash” mode, for example in fully-formulated heavy-dutylaundry detergent granules. Moreover, in addition to the bleachingand/or soil-removing advantages, other advantages of the instantcompositions include their efficacy in improving the sanitary conditionof surfaces ranging from laundered textiles to kitchen counter-tops andbathroom tiles. Without intending to be limited by theory, it isbelieved that the compositions can help control or kill a wide varietyof micro-organisms, including bacteria, viruses, sub-viral particles andmolds; as well as to destroy objectionable non-living proteins and/orpeptides such as certain toxins.

[0265] The transition-metal oxidation catalysts useful herein may besynthesized by any convenient route. However, specific synthesis methodsare nonlimitingly illustrated in detail as follows, including asynthetic method according to the present invention wherein the catalystis prepared under strictly oxygen and hydroxyl-free conditions by use ofbis(pyridine) manganese (II) salts (e.g., chloride salt) to coordinatethe manganese into the macropolycyclic rigid ligand [see, for example,Example 1, Method I, and Example 7].

EXAMPLE 1 Synthesis of [Mn(Bcyclam)Cl₂]

[0266]

[0267] (a) Method I.

[0268] “Bcyclam”(5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane) is preparedby a synthesis method described by G. R. Weisman, et al., J. Amer. Chem.Soc., (1990), 112, 8604. Bcyclam (1.00 g., 3.93 mmol) is dissolved indry CH₃CN (35 mL, distilled from CaH₂). The solution is then evacuatedat 15 mm until the CH₃CN begins to boil. The flask is then brought toatmospheric pressure with Ar. This degassing procedure is repeated 4times. Mn(pyridine)₂Cl₂ (1.12 g., 3.93 mmol), synthesized according tothe literature procedure of H. T. Witteveen et al., J. Inorg. Nucl.Chem., (1974), 36, 1535, is added under Ar. The cloudy reaction solutionslowly begins to darken. After stirring overnight at room temperature,the reaction solution becomes dark brown with suspended fineparticulates. The reaction solution is filtered with a 0.2μ filter. Thefiltrate is a light tan color. This filtrate is evaporated to drynessusing a rotoevaporator. After drying overnight at 0.05 mm at roomtemperature, 1.35 g. off-white solid product is collected, 90% yield.Elemental Analysis: %Mn, 14.45; %C, 44.22; %H, 7.95; theoretical for[Mn(Bcyclam)Cl₂], MnC₁₄H₃₀N₄Cl₂, MW=380.26. Found: %Mn, 14.98; %C,44.48; %H, 7.86; Ion Spray Mass Spectroscopy shows one major peak at 354mu corresponding to [Mn(Bcyclam)(formate)]⁺.

[0269] (b) Method II.

[0270] Freshly distilled Bcyclam (25.00 g., 0.0984 mol), which isprepared by the same method as above, is dissolved in dry CH₃CN (900 mL,distilled from CaH₂). The solution is then evacuated at 15 mm until theCH₃CN begins to boil. The flask is then brought to atmospheric pressurewith Ar. This degassing procedure is repeated 4 times. MnCl₂ (11.25 g.,0.0894 mol) is added under Ar. The cloudy reaction solution immediatelydarkens. After stirring 4 hrs. under reflux, the reaction solutionbecomes dark brown with suspended fine particulates. The reactionsolution is filtered through a 0.2% filter under dry conditions. Thefiltrate is a light tan color. This filtrate is evaporated to drynessusing a rotoevaporator. The resulting tan solid is dried overnight at0.05 mm at room temperature. The solid is suspended in toluene (100 mL)and heated to reflux. The toluene is decanted off and the procedure isrepeated with another 100 mL of toluene. The balance of the toluene isremoved using a rotoevaporator. After drying overnight at 0.05 mm atroom temperature, 31.75 g. of a light blue solid product is collected,93.5% yield. Elemental Analysis: %Mn, 14.45; %C, 44.22; %H, 7.95; %N,14.73; %Cl, 18.65; theoretical for [Mn(Bcyclam)Cl₂], MnC₁₄H₃₀N₄Cl₂,MW=380.26. Found: %Mn, 14.69; %C, 44.69; %H, 7.99; %N, 14.78; %Cl, 18.90(Karl Fischer Water, 0.68%). Ion Spray Mass Spectroscopy shows one majorpeak at 354 mu corresponding to [Mn(Bcyclam)(formate)]⁺.

EXAMPLE 2 Synthesis of [Mn(C₄-Bcyclam)Cl₂] whereC₄-Bcyclam=5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

[0271]

[0272] (a) C₄-Bcyclam Synthesis

[0273] Tetracyclic adduct I is prepared by the literature method of H.Yamamoto and K. Maruoka, J. Amer. Chem. Soc., (1981), 103, 4194. 1 (3.00g., 13.5 mmol) is dissolved in dry CH₃CN (50 mL, distilled from CaH₂).1-lodobutane (24.84 g., 135 mmol) is added to the stirred solution underAr. The solution is stirred at room temperature for 5 days. 4-Iodobutane(12.42 g., 67.5 mmol) is added and the solution is stirred an additional5 days at RT. Under these conditions, I is fully mono-alkylated with1-iodobutane as shown by

[0274]¹³C-NMR. Methyl iodide (26.5 g, 187 mmol) is added and thesolution is stirred at room temperature for an additional 5 days. Thereaction is filtered using Whatman #4 paper and vacuum filtration. Awhite solid, II, is collected (6.05 g., 82%).

[0275]¹³C NMR (CDCl₃) 16.3, 21.3, 21.6, 22.5, 25.8, 49.2, 49.4, 50.1,51.4, 52.6, 53.9, 54.1, 62.3, 63.5, 67.9, 79.1, 79.2 ppm. Electro sprayMass Spec. (MH⁺/2, 147).

[0276] II (6.00 g., 11.0 mmol) is dissolved in 95% ethanol (500 mL).Sodium borohydride (11.0 g., 290 mmol) is added and the reaction turnsmilky white. The reaction is stirred under Ar for three days.Hydrochloric acid (100 mL, concentrated) is slowly dripped into thereaction mixture over 1 hour. The reaction mixture is evaporated todryness using a rotoevaporator. The white residue is dissolved in sodiumhydroxide (500 mL, 1.00N). This solution is extracted with toluene(2×150 mL). The toluene layers are combined and dried with sodiumsulfate. After removal of the sodium sulfate using filtration, thetoluene is evaporated to dryness using a rotoevaporator. The resultingoil is dried at room temperature under high vacuum (0.05 mm) overnight.A colorless oil results 2.95 g., 90%. This oil (2.10 g.) is distilledusing a short path distillation apparatus (still head temperature 115 Cat 0.05 mm). Yield: 2.00 g. ¹³C NMR (CDCl₃) 14.0, 20.6, 27.2, 27.7,30.5, 32.5, 51.2, 51.4, 54.1, 54.7, 55.1, 55.8, 56.1, 56.5, 57.9, 58.0,59.9 ppm. Mass Spec. (MH⁺, 297).

[0277] (b) [Mn(C₄-Bcyclam)Cl₂] Synthesis

[0278] C₄-Bcyclam (2.00 g., 6.76 mmol) is slurried in dry CH₃CN (75 mL,distilled from CaH₂). The solution is then evacuated at 15 mm until theCH₃CN begins to boil. The flask is then brought to atmospheric pressurewith Ar. This degassing procedure is repeated 4 times. MnCl₂ (0.81 g.,6.43 mmol) is added under Ar. The tan, cloudy reaction solutionimmediately darkens, After stirring 4 hrs. under reflux, the reactionsolution becomes dark brown with suspended fine particulates. Thereaction solution is filtered through a 0.2μ membrane filter under dryconditions. The filtrate is a light tan color. This filtrate isevaporated to dryness using a rotoevaporator. The resulting white solidis suspended in toluene (50 mL) and heated to reflux. The toluene isdecanted off and the procedure is repeated with another 100 mL oftoluene. The balance of the toluene is removed using a rotoevaporator.After drying overnight at 0.05 mm, RT, 2.4 g. a light blue solidresults, 88% yield. Ion Spray Mass Spectroscopy shows one major peak at396 mu corresponding to [Mn(C₄-Bcyclam)(formate)]⁺.

EXAMPLE 3 Synthesis of [Mn(Bz-Bcyclam)Cl₂] whereBz-Bcyclam=5-benzyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

[0279]

[0280] (a) Bz-Bcyclam Synthesis

[0281] This ligand is synthesized similarly to the C₄-Bcyclam synthesisdescribed above in Example 2(a) except that benzyl bromide is used inplace of the 1-iodobutane.

[0282]¹³C NMR (CDCl₃) 27.6, 28.4, 43.0, 52.1, 52.2, 54.4, 55.6, 56.4,56.5, 56.9, 57.3, 57.8, 60.2, 60.3, 126.7, 128.0, 129.1, 141.0 ppm. MassSpec. (MH⁺, 331).

[0283] (b) [Mn(Bz-Bcyclam)Cl₂] Synthesis

[0284] This complex is made similarly to the [Mn(C₄-Bcyclam)Cl₂]synthesis described above in Example 2(b) except that Bz-Bcyclam is usedin place of the C4-Bcyclam. Ion Spray Mass Spectroscopy shows one majorpeak at 430 mu corresponding to [Mn(Bz-Bcyclam)(formate)]⁺.

EXAMPLE 4 Synthesis of [Mn(C₈-Bcyclam)Cl₂] whereC₈-Bcyclam=5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

[0285]

[0286] (a) C₈-Bcyclam Synthesis:

[0287] This ligand is synthesized similarly to the C₄-Bcyclam synthesisdescribed above in Example 2(a) except that 1-iodooctane is used inplace of the 1-iodobutane.

[0288] Mass Spec. (MH⁺, 353).

[0289] (b) [Mn(C₈-Bcyclam)Cl₂] Synthesis

[0290] This complex is made similarly to the [Mn(C₄-Bcyclam)Cl₂]synthesis described above in Example 2(b)except that C₈-Bcyclam is usedin place of the C₄-Bcyclam.

[0291] Ion Spray Mass Spectroscopy shows one major peak at 452 mucorresponding to [Mn(B₈-Bcyclam)(formate)]⁺.

EXAMPLE 5 Synthesis of [Mn(H₂-Bcyclam)Cl₂] whereH₂-Bcyclam=1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

[0292]

[0293] The H₂-Bcyclam is synthesized similarly to the C₄-Bcyclamsynthesis described above except that benzyl bromide is used in place ofthe 1-iodobutane and the methyl iodide. The benzyl groups are removed bycatalytic hydrogenation. Thus, the resulting5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane and 10% Pd oncharcoal is dissolved in 85% acetic acid. This solution is stirred 3days at room temperature under 1 atm. of hydrogen gas. The solution isfiltered though a 0.2 micron filter under vacuum. After evaporation ofsolvent using a rotary evaporator, the product is obtained as acolorless oil.

[0294] Yield: 90+%.

[0295] The Mn complex is made similarly to the [Mn(Bcyclam)Cl₂]synthesis described in Example 1(b) except that the that H2-Bcyclam isused in place of the Bcyclam.

[0296] Elemental Analysis: %C, 40.92; %H, 7.44; %N, 15.91; theoreticalfor [Mn(H₂-Bcyclam)Cl₂], MnC₁₂H₂₆N₄Cl₂, MW=352.2. Found: %C, 41.00; %H,7.60; %N, 15.80. FAB+ Mass Spectroscopy shows one major peak at 317 mucorresponding to [Mn(H₂-Bcyclam)Cl]⁺and another minor peak at 352 mucorresponding to [Mn(H₂-Bcyclam)Cl₂]⁺.

EXAMPLE 6 Synthesis of [Fe(H₂-Bcyclam)Cl₂] whereH₂-Bcyclam=1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

[0297]

[0298] The Fe complex is made similarly to the [Mn(H₂-Bcyclam)Cl₂]synthesis described in Example 5 except that the that anhydrous FeCl₂ isused in place of the MnCl₂.

[0299] Elemental Analysis: %C, 40.82; %H, 7.42; %N, 15.87; theoreticalfor [Fe(H₂-Bcyclam)Cl₂], FeC₁₂H₂₆N₄Cl₂, MW=353.1. Found: %C, 39.29; %H,7.49; %N, 15.00. FAB+ Mass Spectroscopy shows one major peak at 318 mucorresponding to [Fe(H₂-Bcyclam)Cl]⁺ and another minor peak at 353 mucorresponding to [Fe(H₂-Bcyclam)Cl₂]⁺.

EXAMPLE 7.

[0300] Synthesis of:

[0301] Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24), 11,13,15(25)-hexaene manganese(II)hexafluorophosphate ,7(b);

[0302] Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene manganese(II) trifluoromethanesulfonate, 7(c) andThiocyanato-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene iron(II) thiocyanate, 7(d)

[0303] (a) Synthesis of the ligand20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^(3,7).1^(11,15).]pentacosa-3,5,7(24),11,13,15(25)-hexaene

[0304] The ligand7-methyl-3,7,11,17-tetraazabicyclo[11.3.1¹⁷]heptadeca-1(17), 13,15-triene is synthesized by the literature procedure of K. P.Balakrishnan et al., J. Chem. Soc., Dalton Trans., 1990, 2965.

[0305] 7-methyl-3,7,11,17-tetraazabicyclo[11.3.1¹⁷]heptadeca-1(17),13,15-triene (1.49 g, 6 mmol) andO,O′-bis(methanesulfonate)-2,6-pyridine dimethanol (1.77 g, 6 mmol) areseparately dissolved in acetonitrile (60 ml). They are then added via asyringe pump (at a rate of 1.2 ml/hour) to a suspension of anhydroussodium carbonate (53 g, 0.5 mol) in acetonitrile (1380 ml). Thetemperature of the reaction is maintained at 65° C. throughout the totalreaction of 60 hours.

[0306] After cooling, the solvent is removed under reduced pressure andthe residue is dissolved in sodium hydroxide solution (200 ml, 4M). Theproduct is then extracted with benzene (6 times 100 ml) and the combinedorganic extracts are dried over anhydrous sodium sulfate. Afterfiltration the solvent is removed under reduced pressure. The product isthen dissolved in an acetonitrile/triethylamine mixture (95:5) and ispassed through a column of neutral alumina (2.5×12 cm). Removal of thesolvent yields a white solid (0.93 g, 44%).

[0307] This product may be further purified by recrystallization from anethanol/diethylether mixture combined with cooling at 0° C. overnight toyield a white crystalline solid. Anal. Calcd. for C₂₁H₂₉N₅: C, 71.75; H,8.32; N, 19.93. Found: C, 71.41; H, 8.00; N, 20.00. A mass spectrumdisplays the expected molecular ion peak [for C₂₁H₃₀N₅]⁺ at m/z=352. The¹H NMR(400 MHz, in CD₃CN) spectrum exhibits peaks at δ=1.81 (m, 4H);2.19 (s, 3H); 2.56 (t, 4H); 3.52 (t, 4H); 3.68 (AB, 4H), 4.13 (AB, 4H),6.53 (d, 4H) and 7.07 (t, 2H). The ¹³C NMR(75.6 MHz, in CD₃CN) spectrumshows eight peaks at δ=24.05, 58.52, 60.95, 62.94, 121.5, 137.44 and159.33 ppm.

[0308] All metal complexation reactions are performed in an inertatmosphere glovebox using distilled and degassed solvents.

[0309] (b) Complexation of the Ligand L₁ with Bis(pyridine) Manganese(II) Chloride

[0310] Bis(pyridine)manganese (II) chloride is synthesized according tothe literature procedure of H. T. Witteveen et al., J. Inorg. Nucl.Chem., 1974, 36, 1535.

[0311] The ligand L₁ (1.24 g, 3.5 mmol), triethylamine(0.35 g, 3.5 mmol)and sodium hexafluorophosphate (0.588 g, 3.5 mmol) are dissolved inpyridine (12 ml). To this is added bis(pyridine)manganese (II) chlorideand the reaction is stirred overnight. The reaction is then filtered toremove a white solid. This solid is washed with acetonitrile until thewashings are no longer colored and then the combined organic filtratesare evaporated under reduced pressure. The residue is dissolved in theminimum amount of acetonitrile and allowed to evaporate overnight toproduce bright red crystals. Yield: 0.8 g (39%). Anal. Calcd. forC₂₁H₃₁N₅Mn₁C₁₁P₁F₆: C, 43.00; H, 4.99 and N, 11.95. Found: C, 42.88; H,4.80 and N 11.86. A mass spectrum displays the expected molecular ionpeak [for C₂₁H₃₁N₅Mn₁Cl₁] at m/z=441. The electronic spectrum of adilute solution in water exhibits two absorption bands at 260 and 414 nm(ε=1.47×10³ and 773 M⁻¹cm⁻¹ respectively). The IR spectrum (KBr) of thecomplex shows a band at 1600 cm⁻¹ (pyridine), and strong bands at 840and 558 cm⁻¹ (PF₆ ⁻).

[0312] (c) Complexation of the Ligand with Manganese (II)Trifluoromethanesulfonate

[0313] Manganese (II) trifluoromethanesulfonate is prepared by theliterature procedure of Bryan and Dabrowiak, Inorg. Chem., 1975, 14,297.

[0314] Manganese (II) trifluoromethanesulfonate (0.883 g, 2.5 mmol) isdissolved in acetonitrile (5 ml). This is added to a solution of theligand L₁ (0.878 g, 2.5 mmol) and triethylamine (0.25 g, 2.5 mmol) inacetonitrile (5 ml). This is then heated for two hours before filteringand then after cooling removal of the solvent under reduced pressure.The residue is dissolved in a minimum amount of acetonitrile and left toevaporate slowly to yield orange crystals. Yield 1.06 g (60%). Anal.Calc. for Mn₁C₂₃H₂₉N₅S₂F₆O₆: C, 39.20; H, 4.15 and N, 9.95. Found: C,38.83; H, 4.35 and N, 10.10. The mass spectrum displays the expectedpeak for [Mn₁C₂₂H₂₉N₅S₁F₃O₃]⁺ at m/z=555. The electronic spectrum of adilute solution in water exhibits two absorption bands at 260 and 412 nm(ε=9733 and 607 M⁻¹cm⁻¹ respectively). The IR spectrum (KBr) of thecomplex shows a band at 1600 cm⁻¹ (pyridine) and 1260, 1160 and 1030cm⁻¹(CF₃SO₃).

[0315] (d) Complexation of the Ligand with Iron (I)Trifluoromethanesulfonate

[0316] Iron (III) trifluoromethanesulfonate is prepared in situ by theliterature procedure Tait and Busch, Inorg. Synth., 1978, XVII, 7.

[0317] The ligand (0.833 g, 2.5 mmol) and triethylamine (0.505 g, 5mmol) are dissolved in acetonitrile (5 ml). To this is added a solutionof hexakis(acetonitrile) iron (11) trifluoromethanesulfonate (1.5 g, 2.5mmol) in acetonitrile (5 ml) to yield a dark red solution. Sodiumthiocyanate (0.406 g, 5 mmol) is then added and the reaction stirred fora further hour. The solvent is then removed under reduced pressure andthe resulting solid is recrystallized from methanol to produce redmicrocrystals. Yield: 0.65 g (50%). Anal. Calc. for Fe₁C₂₃H₂₉N₇S₂: C,52.76; H, 5.59 and N, 18.74. Found: C 52.96; H, 5.53; N, 18.55. A massspectrum displays the expected molecular ion peak [for Fe₁C₂₂H₂₉N₆S₁]⁺at m/z=465. The ¹H NMR (300 MHz, CD₃CN) δ=1.70(AB, 2H), 2.0 (AB, 2H),2.24 (s, 3H), 2.39 (m, 2H), 2.70 (m, 4H), 3.68 (m, 4H), 3.95 (m, 4H),4.2 (AB, 2H), 7.09 (d, 2H), 7.19 (d, 2H), 7.52 (t, 1H), 7.61 (d, 1H).The IR spectrum (KBr) of the spectrum shows peaks at 1608 cm⁻¹(pyridine) and strong peaks at 2099 and 2037 cm⁻¹(SCN⁻). Example8[Mn(Bcyclam)Cl₂] is used in a catalytic system including the transitionmetal complex, water as solvent, and t-butyl peroxide as primaryoxidant, to catalyze the oxidation of a lignin model compound. See U.S.Pat. No. 5,077,394, Example 9, incorporated by reference, for details.The Mn complex replaces the iron porphyrin complex of '394.

EXAMPLE 8

[0318] [Mn(Bcyclam)Cl₂] is used in a catalytic system including thetransition metal complex, dimethylformamide as solvent, and peracetateas primary oxidant, to catalyze the oxidation of lignin. See U.S. Pat.No. 5,077,394, Example 10, incorporated by reference, for details. TheMn complex replaces the iron porphyrin complex of this patent. In moredetail, 250 micrograms of the Kraft softwood lignin Indulin AT (WestvacoCorporation, Charleston Heights, S.C.) is dissolved in 2 ml DMF.Peracetic acid is used as the primary oxidant at a final concentrationof 1.84 micromolar. The Mn complex is used at a final concentration of500 micromolar. The reaction mixture is stirred at room temperature for24 hours and the resulting products are analyzed by gel permeationchromatography; any convenient column and solvent arrangement maysuffice, though a TSK 4000 column with 1:1 chloroform:dioxane(Phenomenex, Rancho Palos Verdes, Calif.) may be useful. Absorbance ismonitored at a suitable wavelength, for example 280 nm, and a distinctshift of the peaked area to the right indicates that a degradation oflignin has occurred.

EXAMPLE 9

[0319] [Mn(Bcyclam)Cl₂] is used in a catalytic system including thetransition metal complex, water, and a range of different primaryoxidants, to catalyze the oxidation of veratryl alcohol toveratrylaldehyde. See U.S. Pat. No. 5,077,394, Example 11, incorporatedby reference, for details. The Mn complex replaces the manganeseporphyrin complex of this patent. The oxidants include hydrogenperoxide, sodium hypochlorite, t-butylhydroperoxide, cumylhydroperoxide,potassium iodate and iodosylbenzene and the experiments are carried outover a range of pH of from 1 to 13 and with a variety of oxidantconcentrations. The product is veratrylaldehyde. Yields tend to varywith pH and time, with evidence of product formation being obtainedunder a variety of conditions including slightly acid (e.g., pH 6.5) tomildly alkaline (e.g., pH 8.5-9). The catalyst effects an improvementover non-catalyzed reaction.

EXAMPLE 10

[0320] [Mn(Bcyclam)Cl₂] is used in a catalytic system including thetransition metal complex, solvent, and primary oxidant, to epoxidizecylohexene. See U.S. Pat. No. 5,077,394, Example 13, incorporated byreference, for one possible procedure. The Mn complex replaces thecomplexes used in this patent.

EXAMPLE 11

[0321] [Mn(Bcyclam)Cl₂] is used in a catalytic system including thetransition metal complex, water as solvent, and hydrogenperoxide/peracetic acid buffered in sodium carbonate/bicarbonate at pHof about 9, to oxidize a blue dye, suitably Chicago Sky Blue 6B(Aldrich), to a colorless product. The reaction can be monitored byultraviolet spectroscopy.

[0322] Oxidation Agents:

[0323] Oxidation agents (sometimes termed “oxidants”) useful in thepresent invention can be any of the oxidizing agents known for oxidativesynthetic reaction chemistry, pulp oxidation and bleaching, laundry,hard surface cleaning, automatic dishwashing or denture cleaningpurposes. Oxygen bleaches or mixtures thereof are preferred, thoughother oxidants, such as oxygen, an enzymatic hydrogen peroxide producingsystem, or hypohalites, such as chlorine oxidants like hypochlorite, mayalso be used. Oxygen-based oxidants deliver “available oxygen” (AvO) or“active oxygen” which is typically measurable by standard methods suchas iodide/thiosulfate and/or ceric sulfate titration. See the well-knownwork by Swern, or Kirk Othmer's Encyclopedia of Chemical Technologyunder “Bleaching Agents”. When the oxidant is a peroxygen compound, itcontains —O—O— linkages with one O in each such linkage being “active”.AvO content of such an oxidant compound, usually expressed as a percent,is equal to 100*the number of active oxygen atoms*(16/molecular weightof the oxygen bleach compound). Preferably, an oxygen bleach will beused herein, since this benefits most directly from combination with thecatalyst. The mode of combination can vary. For example, the catalystand oxidant can be incorporated into a single product formula, or can beused in various combinations of “pretreatment product” such as “stainsticks”, “main wash product” and even “post-wash product” such as fabricconditioners or dryer-added sheets. The oxidant herein can have anyphysical form compatible with the intended application; moreparticularly, liquid-form and solid-form oxidants as well as adjuncts,promoters or activators are included. Liquids can be included in soliddetergents, for example by adsorption onto an inert support; and solidscan be included in liquid detergents, for example by use of compatiblesuspending agents. Common oxidants of the peroxygen type includehydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates andthe organic peroxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids. These can be peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts. Peracids of various kinds can be usedboth in free form and as precursors known as “bleach activators” or“bleach promoters” which, when combined with a source of hydrogenperoxide, perhydrolyze to release the corresponding peracid. Also usefulherein as oxidants are the inorganic peroxides such as Na₂O₂,superoxides such as KO₂, organic hydroperoxides such as cumenehydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacidsand their salts such as the peroxosulfuric acid salts, especially thepotassium salts of peroxodisulfuric acid and, more preferably, ofperoxomonosulfuric acid including the commercial triple-salt form soldas OXONE by Dupont and also any equivalent commercially available formssuch as CUROX from Akzo or CAROAT from Degussa. Certain organicperoxides, such as dibenzoyl peroxide, may be useful, especially asadditives rather than as primary oxygen bleach.

[0324] Mixed oxidants are generally useful, as are mixtures of anyoxidants with the known bleach activators, organic catalysts, enzymaticcatalysts and mixtures thereof; moreover such mixtures may furtherinclude brighteners, photobleaches and dye transfer inhibitors of typeswell-known in the art.

[0325] Preferred oxidants include the peroxohydrates, sometimes known asperoxyhydrates or peroxohydrates. These are organic or, more commonly,inorganic salts capable of releasing hydrogen peroxide rather readily.They include types in which hydrogen peroxide is present as a truecrystal hydrate, and types in which hydrogen peroxide is incorporatedcovalently and is released chemically, for example by hydrolysis.Typically, peroxohydrates deliver hydrogen peroxide readily enough thatit can be extracted in measurable amounts into the ether phase of anether/water mixture. Peroxohydrates are characterized in that they failto give the Riesenfeld reaction, in contrast to certain other oxidanttypes described hereinafter. Peroxohydrates are the most common examplesof “hydrogen peroxide source” materials and include the perborates,percarbonates, perphosphates, and persilicates. Other materials whichserve to produce or release hydrogen peroxide are, of course, useful.Mixtures of two or more peroxohydrates can be used, for example when itis desired to exploit differential solubility. Suitable peroxohydratesinclude sodium carbonate peroxyhydrate and equivalent commercial“percarbonate” oxidants, and any of the so-called sodium perboratehydrates, the “tetrahydrate” and “monohydrate” being preferred; thoughsodium pyrophosphate peroxyhydrate can be used. Many such peroxohydratesare available in processed forms with coatings, such as of silicateand/or borate and/or waxy materials and/or surfactants, or have particlegeometries, such as compact spheres, which improve storage stability. Byway of organic peroxohydrates, urea peroxyhydrate can also be usefulherein.

[0326] Percarbonate oxidant includes, for example, dry particles havingan average particle size in the range from about 500 micrometers toabout 1,000 micrometers, not more than about 10% by weight of saidparticles being smaller than about 200 micrometers and not more thanabout 10% by weight of said particles being larger than about 1,250micrometers. Percarbonates and perborates are widely available incommerce, for example from FMC, Solvay and Tokai Denka.

[0327] Organic percarboxylic acids useful herein as the oxidants includemagnesium monoperoxyphthalate hexahydrate, available from Interox,m-chloro perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyricacid and diperoxydodecanedioic acid and their salts. Such bleaches aredisclosed in U.S. Pat. No. 4,483,781, U.S. patent application Ser. No.740,446, Burns et al, filed Jun. 3, 1985, EP-A 133,354, published Feb.20, 1985, and U.S. 4,412,934. Highly preferred oxidants also include6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Pat.No. 4,634,551 and include those having formula HO—O—C(O)—R—Y wherein Ris an alkylene or substituted alkylene group containing from 1 to about22 carbon atoms or a phenylene or substituted phenylene group, and Y ishydrogen, halogen, alkyl, aryl or —C(O)—OH or —C(O)—O—OH.

[0328] Organic percarboxylic acids usable herein include thosecontaining one, two or more peroxy groups and can be aliphatic oraromatic. When the organic percarboxylic acid is aliphatic, theunsubstituted acid suitably has the linear formula:HO—O—C(O)—(CH₂)_(n)—Y where Y can be, for example, H, CH₃, CH₂Cl, COOH,or C(O)OOH; and n is an integer from 1 to 20. Branched analogs are alsoacceptable. When the organic percarboxylic acid is aromatic, theunsubstituted acid suitably has formula: HO—O—C(O)—C₆H₄—Y wherein Y ishydrogen, alkyl, alkyhalogen, halogen, or —COOH or —C(O)OOH.

[0329] Monoperoxycarboxylic acids useful as oxidant herein are furtherillustrated by alkyl percarboxylic acids and aryl percarboxylic acidssuch as peroxybenzoic acid and ring-substituted peroxybenzoic acids,e.g., peroxy-alpha-naphthoic acid; aliphatic, substituted aliphatic andarylalkyl monoperoxy acids such as peroxylauric acid, peroxystearicacid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and6-octylamino-6-oxo-peroxyhexanoic acid. Monoperoxycarboxylic acids canbe hydrophilic, such as peracetic acid, or can be relativelyhydrophobic. The hydrophobic types include those containing a chain ofsix or more carbon atoms, preferred hydrophobic types having a linearaliphatic C8-C14 chain optionally substituted by one or more etheroxygen atoms and/or one or more aromatic moieties positioned such thatthe peracid is an aliphatic peracid. More generally, such optionalsubstitution by ether oxygen atoms and/or aromatic moieties can beapplied to any of the peracids or bleach activators herein.Branched-chain peracid types and aromatic peracids having one or moreC3-C16 linear or branched long-chain substituents can also be useful.The peracids can be used in the acid form or as any suitable salt with ableach-stable cation. Very useful herein are the organic percarboxylicacids of formula:

[0330] or mixtures thereof wherein R¹ is alkyl, aryl, or alkarylcontaining from about 1 to about 14 carbon atoms, R² is alkylene,arylene or alkarylene containing from about 1 to about 14 carbon atoms,and R⁵ is H or alkyl, aryl, or alkaryl containing from about 1 to about10 carbon atoms. When these peracids have a sum of carbon atoms in R¹and R² together of about 6 or higher, preferably from about 8 to about14, they are particularly suitable as hydrophobic peracids for bleachinga variety of relatively hydrophobic or “lipophilic” stains, includingso-called “dingy” types. Calcium, magnesium, or substituted ammoniumsalts may also be useful.

[0331] Other useful peracids and bleach activators herein are in thefamily of imidoperacids and imido bleach activators. These includephthaloylimidoperoxycaproic acid and related arylimido-substituted andacyloxynitrogen derivatives. For listings of such compounds,preparations and their incorporation into laundry compositions includingboth granules and liquids, See U.S. Pat. Nos. 5,487,818; 5,470,988,5,466,825; 5,419,846; 5,415,796; 5,391,324; 5,328,634; 5,310,934;5,279,757; 5,246,620; 5,245,075; 5,294,362; 5,423,998; 5,208,340;5,132,431 and 5,087,385.

[0332] Useful diperoxyacids include, for example,1,12-diperoxydodecanedioic acid (DPDA); 1,9-diperoxyazelaic acid;diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalicacid; 2-decyldiperoxybutane-1,4-dioic acid; and4,4′-sulphonylbisperoxybenzoic acid. Owing to structures in which tworelatively hydrophilic groups are disposed at the ends of the molecule,diperoxyacids have sometimes been classified separately from thehydrophilic and hydrophobic monoperacids, for example as “hydrotropic”:Some of the diperacids are hydrophobic in a quite literal sense,especially when they have a long-chain moiety separating the peroxyacidmoieties.

[0333] More generally, the terms “hydrophilic” and “hydrophobic” usedherein in connection with any of the oxidants, especially the peracids,and in connection with bleach activators, are in the first instancebased on whether a given oxidant effectively performs bleaching offugitive dyes in solution thereby preventing fabric greying anddiscoloration and/or removes more hydrophilic stains such as tea, wineand grape juice—in this case it is termed “hydrophilic”. When theoxidant or bleach activator has a significant stain removal,whiteness-improving or cleaning effect on dingy, greasy, carotenoid, orother hydrophobic soils, it is termed “hydrophobic”. The terms areapplicable also when referring to peracids or bleach activators used incombination with a hydrogen peroxide source. The current commercialbenchmarks for hydrophilic performance of oxidant systems are: TAED orperacetic acid, for benchmarking hydrophilic bleaching. NOBS or NAPAAare the corresponding benchmarks for hydrophobic bleaching. The terms“hydrophilic”, “hydrophobic” and “hydrotropic” with reference tooxidants including peracids and here extended to bleach activator havealso been used somewhat more narrowly in the literature. See especiallyKirk Othmer's Encyclopedia of Chemical Technology, Vol. 4., pages284-285. This reference provides a chromatographic retention time andcritical micelle concentration-based set of criteria, and is useful toidentify and/or characterize preferred sub-classes of hydrophobic,hydrophilic and hydrotropic oxidants and bleach activators that can beused in the present invention.

[0334] Bleach Activators

[0335] Bleach activators useful herein include amides, imides, estersand anhydrides. Commonly at least one substituted or unsubstituted acylmoiety is present, covalently connected to a leaving group as in thestructure R—C(O)—L. In one preferred mode of use, bleach activators arecombined with a source of hydrogen peroxide, such as the perborates orpercarbonates, in a single product. Conveniently, the single productleads to in situ production in aqueous solution (i.e., during thewashing process) of the percarboxylic acid corresponding to the bleachactivator. The product itself can be hydrous, for example a powder,provided that water is controlled in amount and mobility such thatstorage stability is acceptable. Alternately, the product can be ananhydrous solid or liquid. In another mode, the bleach activator oroxygen bleach is incorporated in a pretreatment product, such as a stainstick; soiled, pretreated substrates can then be exposed to furthertreatments, for example of a hydrogen peroxide source. With respect tothe above bleach activator structure RC(O)L, the atom in the leavinggroup connecting to the peracid-forming acyl moiety R(C)O— is mosttypically O or N. Bleach activators can have non-charged, positively ornegatively charged peracid-forming moieties and/or noncharged,positively or negatively charged leaving groups. One or moreperacid-forming moieties or leaving-groups can be present. See, forexample, U.S. Pat. Nos. 5,595,967, 5,561,235, 5,560,862 or thebis-(peroxy-carbonic) system of U.S. Pat. No. 5,534,179. Bleachactivators can be substituted with electron-donating orelectron-releasing moieties either in the leaving-group or in theperacid-forming moiety or moieties, changing their reactivity and makingthem more or less suited to particular pH or wash conditions. Forexample, electron-withdrawing groups such as NO₂ improve the efficacy ofbleach activators intended for use in mild-pH (e.g., from about 7.5- toabout 9.5) wash conditions.

[0336] Cationic bleach activators include quaternary carbamate-,quaternary carbonate-, quaternary ester- and quaternary amide-types,delivering a range of cationic peroxyimidic, peroxycarbonic orperoxycarboxylic acids to the wash. An analogous but non-cationicpalette of bleach activators is available when quaternary derivativesare not desired. In more detail, cationic activators include quaternaryammonium-substituted activators of WO 96-06915, U.S. Pat. Nos. 4,751,015and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520 including2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate-(SPCC);N-octyl,N,N-dimethyl-N 10-carbophenoxy decyl ammonium chloride-(ODC);3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate;and N,N,N-trimethyl ammonium toluyloxy benzene sulfonate. Also usefulare cationic nitrites as disclosed in EP-A-303,520 and in EuropeanPatent Specification 458,396 and 464,880. Other nitrile types haveelectron-withdrawing substituents as described in U.S. Pat. No.5,591,378; examples including 3,5-dimethoxybenzonitrile and3,5-dinitrobenzonitrile.

[0337] Other bleach activator disclosures include GB 836,988; 864,798;907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393, and the phenol sulfonate ester ofalkanoyl aminoacids disclosed in U.S. Pat. No. 5,523,434. Suitablebleach activators include any acetylated diamine types, whetherhydrophilic or hydrophobic in character.

[0338] Of the above classes of bleach precursors, preferred classesinclude the esters, including acyl phenol sulfonates, acyl alkyl phenolsulfonates or acyl oxybenzenesulfonates (OBS leaving-group); theacyl-amides; and the quaternary ammonium substituted peroxyacidprecursors including the cationic nitrites.

[0339] Preferred bleach activators include N,N,N′N′-tetraacetyl ethylenediamine (TAED) or any of its close relatives including the triacetyl orother unsymmetrical derivatives. TAED and the acetylated carbohydratessuch as glucose pentaacetate and tetraacetyl xylose are preferredhydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, also has some utility, as does phenylbenzoate.

[0340] Preferred hydrophobic bleach activators include sodiumnonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide typesdescribed in detail hereinafter, such as activators related to NAPAA,and activators related to certain imidoperacid bleaches, for example asdescribed in U.S. Pat. No. 5,061,807, issued Oct. 29, 1991 and assignedto Hoechst Aktiengesellschaft of Frankfurt, Germany. Japanese Laid-OpenPatent Application (Kokai) No. 4-28799 for example describes a bleachingagent and a bleaching detergent composition comprising an organicperacid precursor described by a general formula and illustrated bycompounds which may be summarized more particularly as conforming to theformula:

[0341] wherein L is sodium p-phenolsulfonate, R¹ is CH₃ or C₁₂H₂₅ and R²is H. Analogs of these compounds having any of the leaving-groupsidentified herein and/or having R1 being linear or branched C6-C16 arealso useful.

[0342] Another group of peracids and bleach activators herein are thosederivable from acyclic imidoperoxycarboxylic acids and salts thereof ofthe formula:

[0343] cyclic imidoperoxycarboxylic acids and salts thereof of theformula

[0344] and (iii) mixtures of said compounds, (i) and (ii);

[0345] wherein M is selected from hydrogen and bleach-compatible cationshaving charge q; and y and z are integers such that said compound iselectrically neutral; E, A and X comprise hydrocarbyl groups; and saidterminal hydrocarbyl groups are contained within E and A. The structureof the corresponding bleach activators is obtained by deleting theperoxy moiety and the metal and replacing it with a leaving-group L,which can be any of the leaving-group moieties defined elsewhere herein.In preferred embodiments, there are encompassed detergent compositionswherein, in any of said compounds, X is linear C₃-C₈ alkyl; A isselected from:

[0346] wherein n is from 0 to about 4, and

[0347] wherein R¹ and E are said terminal hydrocarbyl groups, R², R³ andR⁴ are independently selected from H, C₁-C₃ saturated alkyl, and C₁-C₃unsaturated alkyl; and wherein said terminal hydrocarbyl groups arealkyl groups comprising at least six carbon atoms, more typically linearor branched alkyl having from about 8 to about 16 carbon atoms.

[0348] Other suitable bleach activators include sodium-4-benzoyloxybenzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxybenzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate (SPCC);trimethyl ammonium toluyloxy-benzene sulfonate; or sodium3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).

[0349] Bleach activators may be used in an amount of up to 20%,preferably from 0.1-10% by weight, of the composition, though higherlevels, 40% or more, are acceptable, for example in highly concentratedbleach additive product forms or forms intended for appliance automateddosing.

[0350] Highly preferred bleach activators useful herein areamide-substituted and have either of the formulae:

[0351] or mixtures thereof, wherein R¹ is alkyl, aryl, or alkarylcontaining from about 1 to about 14 carbon atoms including bothhydrophilic types (short R¹) and hydrophobic types (R¹ is especiallyfrom about 8 to about 12), R² is alkylene, arylene or alkarylenecontaining from about 1 to about 14 carbon atoms, R⁵ is H, or an alkyl,aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and Lis a leaving group.

[0352] A leaving group as defined herein is any group that is displacedfrom the bleach activator as a consequence of attack by perhydroxide orequivalent reagent capable of liberating a more potent bleach from thereaction. Perhydrolysis is a term used to describe such reaction. Thusbleach activators perhydrolyze to liberate peracid. Leaving groups ofbleach activators for relatively low-pH washing are suitablyelectron-withdrawing. Preferred leaving groups have slow rates ofreassociation with the moiety from which they have been displaced.Leaving groups of bleach activators are preferably selected such thattheir removal and peracid formation are at rates consistent with thedesired application, e.g., a wash cycle. In practice, a balance isstruck such that leaving-groups are not appreciably liberated, and thecorresponding activators do not appreciably hydrolyze or perhydrolyze,while stored in a bleaching composition. The pK of the conjugate acid ofthe leaving group is a measure of suitability, and is typically fromabout 4 to about 16, preferably from about 6 to about 12, morepreferably from about 8 to about 11.

[0353] Preferred bleach activators include those of the formulae, forexample the amide-substituted formulae, hereinabove, wherein R¹, R² andR⁵ are as defined for the corresponding peroxyacid and L is selectedfrom the group consisting of:

[0354] and mixtures thereof, wherein R¹ is a linear or branched alkyl,aryl, or alkaryl group containing from about 1 to about 14 carbon atoms,R³ is an alkyl chain containing from 1 to about 8 carbon atoms, R⁴ is Hor R³, and Y is H or a solubilizing group. These and other known leavinggroups are, more generally, general suitable alternatives forintroduction into any bleach activator herein. Preferred solubilizinggroups include —SO₃ ⁻M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺, —N⁺(R)₄X⁻ and O←N(R³)₂,more preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁺ wherein R³ is an alkyl chaincontaining from about 1 to about 4 carbon atoms, M is a bleach-stablecation and X is a bleach-stable anion, each of which is selectedconsistent with maintaining solubility of the activator. Under somecircumstances, for example solid-form European heavy-duty granulardetergents, any of the above bleach activators are preferably solidshaving crystalline character and melting-point above about 50 deg. C; inthese cases, branched alkyl groups are preferably not included in theoxygen bleach or bleach activator; in other formulation contexts, forexample heavy-duty liquids with bleach or liquid bleach additives,low-melting or liquid bleach activators are preferred. Melting-pointreduction can be favored by incorporating branched, rather than linearalkyl moieties into the oxygen bleach or precursor.

[0355] When solubilizing groups are added to the leaving group, theactivator can have good water-solubility or dispersibility while stillbeing capable of delivering a relatively hydrophobic peracid.Preferably, M is alkali metal, ammonium or substituted ammonium, morepreferably Na or K, and X is halide, hydroxide, methylsulfate oracetate. Solubilizing groups can, more generally, be used in any bleachactivator herein. Bleach activators of lower solubility, for examplethose with leaving group not having a solubilizing group, may need to befinely divided or dispersed in bleaching solutions for acceptableresults.

[0356] Preferred bleach activators also include those of the abovegeneral formula wherein L is selected from the group consisting of:

[0357] wherein R is as defined above and Y is —SO₃ ⁻M⁺ or —CO₂ ⁻M⁺wherein M is as defined above.

[0358] Preferred examples of bleach activators of the above formulaeinclude (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, andmixtures thereof.

[0359] Other useful activators, disclosed in U.S. Pat. No. 4,966,723,are benzoxazin-type, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety—C(O)OC(R¹)═N—.

[0360] Depending on the activator and precise application, goodbleaching results can be obtained from bleaching systems having within-use pH of from about 6 to about 13, preferably from about 9.0 toabout 10.5. Typically, for example, activators with electron-withdrawingmoieties are used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

[0361] Acyl lactam activators are very useful herein, especially theacyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams(see U.S. Pat. No. 5,503,639) of the formulae:

[0362] wherein R⁶ is H, alkyl, aryl, alkoxyaryl, an alkaryl groupcontaining from 1 to about 12 carbon atoms, or substituted phenylcontaining from about 6 to about 18 carbons. See also U.S. Pat. No.4,545,784 which discloses acyl caprolactams, including benzoylcaprolactam adsorbed into sodium perborate. In certain preferredembodiments of the invention, NOBS, lactam activators, imide activatorsor amide-functional activators, especially the more hydrophobicderivatives, are desirably combined with hydrophilic activators such asTAED, typically at weight ratios of hydrophobic activator: TAED in therange of 1:5 to 5:1, preferably about 1:1. Other suitable lactamactivators are alpha-modified, see WO 96-22350 A1, Jul. 25, 1996. Lactamactivators, especially the more hydrophobic types, are desirably used incombination with TAED, typically at weight ratios of amido-derived orcaprolactam activators: TAED in the range of 1:5 to 5:1, preferablyabout 1:1. See also the bleach activators having cyclic amidineleaving-group disclosed in U.S. Pat. No. 5,552,556.

[0363] Nonlimiting examples of additional activators useful herein areto be found in U.S. Pat. No. 4,915,854, 4,412,934 and 4,634,551. Thehydrophobic activator nonanoyloxybenzene sulfonate (NOBS) and thehydrophilic tetraacetyl ethylene diamine (TAED) activator are typical,and mixtures thereof can also be used.

[0364] The superior bleaching/cleaning action of the presentcompositions is also preferably achieved with safety to natural rubbermachine parts, for example of certain european washing appliances (seeWO 94-28104) and other natural rubber articles, including fabricscontaining natural rubber and natural rubber elastic materials.Complexities of bleaching mechanisms are legion and are not completelyunderstood.

[0365] Additional activators useful herein include those of U.S. Pat.No. 5,545,349. Examples include esters of an organic acid and ethyleneglycol, diethylene glycol or glycerin, or the acid imide of an organicacid and ethylenediamine; wherein the organic acid is selected frommethoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid,ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid,propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid,butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid,2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid,2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid,2-(2-ethoxyethoxy)propionic acid, p-(2-ethoxyethoxy)benzoic acid,2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid,2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyaceticacid,2-propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid,2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid,2-(2-methoxyethoxy)ethoxyacetic acid,2-(2-methoxy-1-methylethoxy)ethoxyacetic acid,2-(2-methoxy-2-methylethoxy)ethoxyacetic acid and2-(2-ethoxyethoxy)ethoxyacetic acid.

[0366] Enzymatic Sources of Hydrogen Peroxide

[0367] On a different track from the bleach activators illustratedhereinabove, another suitable hydrogen peroxide generating system is acombination of a C₁-C₄ alkanol oxidase and a C₁-C₄ alkanol, especially acombination of methanol oxidase (MOX) and ethanol. Such combinations aredisclosed in WO 94/03003. Other enzymatic materials related tobleaching, such as peroxidases, haloperoxidases, oxidases, superoxidedismutases, catalases and their enhancers or, more commonly, inhibitors,may be used as optional ingredients in the instant compositions.

[0368] Oxygen Transfer Agents and Precursors

[0369] Also useful herein are any of the known organic bleach catalysts,oxygen transfer agents or precursors therefor. These include thecompounds themselves and/or their precursors, for example any suitableketone for production of dioxiranes and/or any of the hetero-atomcontaining analogs of dioxirane precursors or dioxiranes, such assulfonimines R¹R²C═NSO₂R³, see EP 446 982 A, published 1991 andsulfonyloxaziridines, for example:

[0370] see EP 446,981 A, published 1991. Preferred examples of suchmaterials include hydrophilic or hydrophobic ketones, used especially inconjunction with monoperoxysulfates to produce dioxiranes in situ,and/or the imines described in U.S. Pat. No. 5,576,282 and referencesdescribed therein. Oxygen bleaches preferably used in conjunction withsuch oxygen transfer agents or precursors include percarboxylic acidsand salts, percarbonic acids and salts, peroxymonosulfuric acid andsalts, and mixtures thereof. See also U.S. Pat. Nos. 5,360,568;5,360,569; and 5,370,826.

[0371] Catalytic System Combinations

[0372] While the combinations of ingredients used with thetransition-metal. bleach catalysts of the invention can be widelypermuted, some particularly preferred combinations include:

[0373] (a) transition metal bleach catalyst +hydrogen peroxide sourcealone, e.g., sodium perborate or percarbonate;

[0374] (b) as (a) but with the further addition of a bleach activatorselected from

[0375] (i) hydrophilic bleach activators;

[0376] (ii) hydrophobic bleach activators and

[0377] (iii) mixtures thereof;

[0378] (c) transition metal bleach catalyst+peracid alone, e.g.,

[0379] (i) hydrophilic peracid, e.g., peracetic acid;

[0380] (ii) hydrophobic peracid, e.g., NAPAA or peroxylauric acid;

[0381] (iii) inorganic peracid, e.g., peroxymonosulfuric acid K salts;

[0382] (d) use (a), (b) or (c) with the further addition of an oxygentransfer agent or

[0383] precursor therefor; especially (c) +oxygen transfer agent.

[0384] Any of (a)-(d) can be further combined with one or more polymericdispersants, sequestrants, antioxidants, fluorescent whitening agents,photobleaches and/or dye transfer inhibitors. In such combinations, thetransition metal bleach catalyst will preferably be at levels in a rangesuited to provide wash (in-use) concentrations of from about 0.1 toabout 10 ppm (weight of catalyst); the other components being used attheir known levels which may vary widely.

[0385] While there is currently no certain advantage, the transitionmetal catalysts of the invention can be used in combination withheretofore-disclosed transition metal bleach or dye transfer inhibitioncatalysts, such as the Mn or Fe complexes of triazacyclononanes, the Fecomplexes of N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine(U.S. Pat. No. 5,580,485) and the like. For example, when the transitionmetal bleach catalyst is one disclosed to be particularly effective forsolution bleaching and dye transfer inhibition, as is the case forexample with certain transition metal complexes of porphyrins, it may becombined with one better suited for promoting interfacial bleaching ofsoiled substrates.

[0386] Laundry and Cleaning Compositions and Methods:

[0387] In general, a laundry or cleaning adjunct is any materialrequired to transform a composition containing only transition-metalbleach catalyst into a composition useful for laundry or cleaningpurposes. Adjuncts in general include detersive surfactants, builders,enzymes, and like materials having an independent cleaning function; andalso stabilizers, diluents, structuring materials, agents havingaesthetic effect such as colorant, pro-perfumes and perfumes. Inpreferred embodiments, laundry or cleaning adjuncts are readilyrecognizable to those of skill in the art as being characteristic oflaundry or cleaning products, especially of laundry or cleaning productsintended for direct use by a consumer in a domestic environment.

[0388] In a hard surface cleaning or fabric laundering operation whichuses the present invention catalytic systems, the target substrate willtypically be a fabric or surface stained with, for example, various foodstains.

[0389] In the case of use in laundry or hard surface catalytic systemsor methods, the catalytically effective amount of transition-metaloxidation catalyst is that sufficient to enhance the appearance of asoiled surface. In such cases, the appearance is typically improved inone or more of whiteness, brightness and de-staining; and acatalytically effective amount is one requiring less than astoichiometric number of moles of catalyst when compared with the numberof moles of primary oxidant, such as hydrogen peroxide or hydrophobicperacid, required to produce measurable effect. In addition to directobservation of the bulk surface being bleached or cleaned, catalyticbleaching effect can (where appropriate) be measured indirectly, such asby measurement of the kinetics or end-result of oxidizing a dye insolution.

[0390] By “effective amount” in a laundry or cleaning adjunct context ismeant an amount of a material, such as a detergent adjunct, which issufficient under whatever comparative or use conditions are employed, toprovide the desired end-result benefit, for example in laundry andcleaning methods to improve the appearance of a soiled surface in one ormore use cycles. A “use cycle” is, for example, one wash of a bundle offabrics by a consumer. Appearance or visual effect can be measured bythe consumer, by technical observers such as trained panelists, or bytechnical instrument means such as spectroscopy or image analysis.

[0391] Unless otherwise indicated, the detergent or detergent additivecompositions may be formulated as granular or power-form all-purpose or“heavy-duty” washing agents, especially laundry detergents; liquid, gelor paste-form all-purpose washing agents, especially the so-calledheavy-duty liquid types; liquid fine-fabric detergents; hand dishwashingagents or light duty dishwashing agents, especially those of thehigh-foaming type; machine dishwashing agents, including the varioustabletted, granular, liquid and rinse-aid types for household andinstitutional use; liquid cleaning and disinfecting agents, includingantibacterial hand-wash types, laundry bars, mouthwashes, denturecleaners, car or carpet shampoos, bathroom cleaners; hair shampoos andhair-rinses; shower gels and foam baths and metal cleaners; as well ascleaning auxiliaries such as bleach additives and “stain-stick” orpre-treat types.

[0392] Catalytic systems herein as incorporated into detergents caninclude boron-free, phosphate-free, or chlorine-free embodiments.

[0393] Desirable adjuncts more generally include detersive surfactants,builders, enzymes, dispersant polymers, color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides,alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizingagents, perfumes, solubilizing agents, carriers, processing aids,pigments, and, for liquid formulations, solvents, as described in detailhereinafter.

[0394] Quite typically, laundry or cleaning compositions herein such aslaundry detergents, laundry detergent additives, hard surface cleaners,automatic dishwashing detergents, synthetic and soap-based laundry bars,fabric softeners and fabric treatment liquids, solids and treatmentarticles of all kinds will require several adjuncts, though certainsimply formulated products, such as bleach additives, may require onlymetal catalyst and a single supporting material such as a detergentbuilder or surfactant which helps to make the potent catalyst availableto the consumer in a manageable dose.

[0395] Catalyst system compositions of the present invention useful forlaundry or cleaning products comprise transition-metal bleach catalystcomprising a complex of a transition metal and a macropolycyclic rigidligand as defined herein. The compositions also comprise at least oneadjunct material, preferably comprising an oxygen bleaching agent suchas a source of hydrogen peroxide. More preferably, the adjunct componentincludes both an oxygen bleaching agent and at least one other adjunctmaterial selected from non-bleaching adjuncts suited for laundrydetergents or cleaning products. Non-bleaching adjuncts as definedherein are adjuncts useful in detergents and cleaning products whichneither bleach on their own, nor are recognized as adjuncts used incleaning primarily as promoters of bleaching such as is the case withbleach activators, organic bleach catalysts or peracids. Preferrednon-bleaching adjuncts include detersive surfactants, detergentbuilders, non-bleaching enzymes having a useful function in detergents,and the like. Preferred cleaning compositions herein can incorporate asource of hydrogen peroxide which is any common hydrogen-peroxidereleasing salt, such as sodium perborate, sodium percarbonate, andmixtures thereof. Also useful are other sources of available oxygen suchas persulfate (e.g., OXONE, manufactured by DuPont), as well aspreformed organic peracids.

[0396] In a hard surface cleaning or fabric laundering operation whichuses the present invention compositions, the target substrate, that is,the material to be cleaned, will typically be a fabric or surfacestained with, for example, various hydrophilic food stains, such ascoffee, tea or wine; with hydrophobic stains such as greasy orcarotenoid stains; or is a “dingy” surface, for example one yellowed bythe presence of a relatively uniformly distributed fine residue ofhydrophobic soils.

[0397] In the preferred laundry compositions, adjuncts such as buildersincluding zeolites and phosphates, surfactants such as anionic and/ornonionic and/or cationic surfactants, dispersant polymers (which modifyand inhibit crystal growth of calcium and/or magnesium salts), chelants(which control wash water introduced transition metals), alkalis (toadjust pH), and detersive enzymes are present. Additionalbleach-modifying adjuncts such as conventional bleach activators such asTAED and/or NOBS may be added, provided that any such materials aredelivered in such a manner as to be compatible with the purposes of thepresent invention. The present detergent or detergent-additivecompositions may, moreover, comprise one or more processing aids,fillers, perfumes, conventional enzyme particle-making materialsincluding enzyme cores or “nonpareils”, as well as pigments, and thelike. In the preferred laundry compositions, additional ingredients suchas soil release polymers, brighteners, and/or dye transfer inhibitorscan be present.

[0398] The inventive compositions can include laundry detergents,hard-surface cleaners and the like which include all the componentsneeded for cleaning; alternatively, the compositions can be made for useas cleaning additives. A cleaning additive, for example, can be acomposition containing the transition-metal bleach catalyst, a detersivesurfactant, and a builder, and can be sold for use as an “add-on”, to beused with a conventional detergent which contains a perborate,percarbonate, or other primary oxidant. The compositions herein caninclude automatic dishwashing compositions (ADD) and denture cleaners,thus, they are not, in general, limited to fabric washing.

[0399] In general, adjunct materials used for the production of ADDcompositions herein are preferably checked for compatibility withspotting/filming on glassware. Test methods for spotting/filming aregenerally described in the automatic dishwashing detergent literature,including DIN test methods. Certain oily materials, especially thosehaving longer hydrocarbon chain lengths, and insoluble materials such asclays, as well as long-chain fatty acids or soaps which form soap scumare therefore preferably limited or excluded from such compositions.

[0400] Amounts of the essential ingredients can vary within wide ranges,however preferred cleaning compositions herein (which have a 1% aqueoussolution pH of from about 6 to about 13, more preferably from about 7.5to about 11.5, and most preferably less than about 11, especially fromabout 9 to about 10.5) are those wherein there is present: from about0.01 ppm to about 500 ppm of a transition-metal bleach catalyst inaccordance with the invention, and the balance, typically from at leastabout 90% to about 100% of one or more laundry or cleaning adjuncts. Inpreferred embodiments, there can be present (also expressed as apercentage by weight of the entire composition) from 0.1% to about 90%,preferably from about 0.5% to about 50% of a primary oxidant, such as apreformed peracid or a source of hydrogen peroxide; from 0% to about20%, preferably at least about 0.001%, of a conventionalbleach-promoting adjunct, such as a hydrophilic bleach activator, ahydrophobic bleach activator, or a mixture of hydrophilic andhydrophobic bleach activators, and at least about 0.001%, preferablyfrom about 1% to about 40%, of a laundry or cleaning adjunct which doesnot have a primary role in bleaching, such as a detersive surfactant, adetergent builder, a detergent enzyme, a stabilizer, a detergent buffer,or mixtures thereof. Such fully-formulated embodiments desirablycomprise, by way of non-bleaching adjuncts, from about 0.1% to about 15%of a polymeric dispersant, from about 0.01% to about 10% of a chelant,and from about 0.00001% to about 10% of a detersive enzyme thoughfurther additional or adjunct ingredients, especially colorants,perfumes, pro-perfumes (compounds which release a fragrance whentriggered by any suitable trigger such as heat, enzyme action, or changein pH) may be present. Preferred adjuncts herein are selected frombleach-stable types, though bleach-unstable types can often be includedthrough the skill of the formulator.

[0401] Detergent compositions herein can have any desired physical form;when in granular form, it is typical to limit water content, for exampleto less than about 10%, preferably less than about 7% free water, forbest storage stability. However, liquid forms using both aqueous and/ornonaqueous solvents are also included.

[0402] Further, preferred compositions of this invention include thosewhich are substantially free of chlorine bleach. By “substantially free”of chlorine bleach is meant that the formulator does not deliberatelyadd a chlorine-containing bleach additive, such as hypochlorite or asource thereof, such as a chlorinated isocyanurate, to the preferredcomposition. However, it is recognized that because of factors outsidethe control of the formulator, such as chlorination of the water supply,some non-zero amount of chlorine bleach may be present in the washliquor. The term “substantially free” can be similarly constructed withreference to preferred limitation of other ingredients, such asphosphate builder.

[0403] In a fabric laundering operation, the target substrate willtypically be a fabric stained with, for example, various food stains.The test conditions will vary, depending on the type of washingappliance used and the habits of the user. Thus, front-loading laundrywashing machines of the type employed in Europe generally use less waterand higher detergent concentrations than do top-loading U.S.-stylemachines. Some machines have considerably longer wash cycles thanothers. Some users elect to use very hot water; others use warm or evencold water in fabric laundering operations. Of course, the catalyticperformance of the transition-metal bleach catalyst will be affected bysuch considerations, and the levels of transition-metal bleach catalystused in fully-formulated detergent and bleach compositions can beappropriately adjusted. As a practical matter, and not by way oflimitation, the compositions and processes herein can be adjusted toprovide on the order of at least one part per ten million of the activetransition-metal bleach catalyst, in the aqueous washing liquor, andwill preferably provide from about 0.01 ppm to about 1.0 ppm, morepreferably from about 0.03 ppm to about 0.6 ppm, of the transition-metalbleach catalyst, in the laundry liquor. To illustrate this pointfurther, on the order of 3 micromolar transition-metal bleach catalystis effective at 40° C., pH 10 under European conditions using perborateand a bleach activator (e.g., nonanoyloxybenzenesulfonate). An increasein concentration of 3-5 fold may be required under U.S. conditions toachieve the same results. Conversely, use of a bleach activator and thetransition-metal bleach catalyst with perborate may allow the formulatorto achieve equivalent bleaching at lower perborate usage levels thanproducts without the transition-metal bleach catalyst.

[0404] The bulk density of granular detergent compositions in accordancewith the present invention typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter. Bulk densityis measured by means of a simple funnel and cup device consisting of aconical funnel molded rigidly on a base and provided with a flap valveat its lower extremity to allow the contents of the funnel to be emptiedinto an axially aligned cylindrical cup disposed below the funnel. Thefunnel is 130 mm high and has internal diameters of 130 mm and 40 mm atits respective upper and lower extremities. It is mounted so that thelower extremity is 140 mm above the upper surface of the base. The cuphas an overall height of 90 mm, an internal height of 87 mm and aninternal diameter of 84 mm. Its nominal volume is 500 ml.

[0405] To carry out a measurement, the funnel is filled with powder byhand pouring, the flap valve is opened and powder allowed to overfillthe cup. The filled cup is removed from the frame and excess powderremoved from the cup by passing a straight edged implement e.g.; aknife, across its upper edge. The filled cup is then weighed and thevalue obtained for the weight of powder doubled to provide a bulkdensity in g/liter. Replicate measurements are made as required.

[0406] The instant compositions may include a detersive surfactant as apreferred component. Detersive surfactants are extensively illustratedin U.S. Pat. No. 3,929,678, Dec. 30, 1975 Laughlin, et al, and U.S. Pat.No. 4,259,217, Mar. 31, 1981, Murphy; in the series “SurfactantScience”, Marcel Dekker, Inc., New York and Basel; in “Handbook ofSurfactants”, M. R. Porter, Chapman and Hall, 2nd Ed., 1994; in“Surfactants in Consumer Products”, Ed. J. Falbe, Springer-Verlag, 1987;and in numerous detergent-related patents assigned to Procter & Gambleand other detergent and consumer product manufacturers. The preferreddetersive surfactant herein therefore includes anionic, nonionic,zwitterionic or amphoteric types of surfactant known for use as cleaningagents in textile laundering. Detersive surfactants useful herein aretypically present at levels from 1% to 55%, by weight.

[0407] Preferred detersive surfactants are: acid, sodium and ammoniumC₉-C₂₀ alkylbenzenesulfonates, particularly sodium linear secondaryalkyl C₁₀-C₁₅ benzenesulfonates (1), including straight-chain andbranched forms; olefinsulfonate salts, (2), that is, material made byreacting olefins, particularly C₁₀-C₂₀ α-olefins, with sulfur trioxideand then neutralizing and hydrolyzing the reaction product; sodium andammonium C₇-C₁₂ dialkyl sulfosuccinates, (3); alkane monosulfonates,(4), such as those derived by reacting C₈-C₂₀ α-olefins with sodiumbisulfite and those derived by reacting paraffins with SO₂ and C₁₂ andthen hydrolyzing with a base to form a random sulfonate; α-Sulfo fattyacid salts or esters, (10); sodium alkylglycerylsulfonates, (11),especially those ethers of the higher alcohols derived from tallow orcoconut oil and synthetic alcohols derived from petroleum; alkyl oralkenyl sulfates, (15), which may be primary or secondary, saturated orunsaturated, branched or unbranched. Such compounds when branched can berandom or regular. When secondary, they preferably have formulaCH₃(CH₂)_(x)(CHOSO₃ M⁺)CH₃ or CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where x and(y+1) are integers of at least 7, preferably at least 9 and M is awater-soluble cation, preferably sodium. When unsaturated, sulfates suchas oleyl sulfate are preferred, while the sodium and ammonium alkylsulfates, especially those produced by sulfating C8-C18 alcohols,produced for example from tallow or coconut oil are also useful; alsopreferred are the alkyl or alkenyl ether sulfates, (16), especially theethoxy sulphates having about 0.5 moles or higher of ethoxylation,preferably from 0.5-8; the alkylethercarboxylates, (19), especially theEO 1-5 ethoxycarboxylates; soaps or fatty acids (21), preferably themore water-soluble types; aminoacid-type surfactants, (23), such assarcosinates, especially oleyl sarcosinate; phosphate esters, (26);alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30),especially the ethoxylates “AE”, including the so-called narrow peakedalkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates as well as theproducts of aliphatic primary or secondary linear or branched C₈-C₁₈alcohols with ethylene oxide, generally 2-30 EO; N-alkyl polyhydroxyfatty acid amides especially the C₁₂-C₁₈ N-methylglucamides, (32), seeWO 9206154, and N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N-(3-methoxypropyl) glucamide while N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing; alkyl polyglycosides, (33);amine oxides, (40), preferably alkyldimethylamine N-oxides and theirdihydrates; sulfobetaines or “sultaines”, (43); betaines (44); andgemini surfactants.

[0408] Preferred levels of anionic detersive surfactants herein are inthe range from about 3% to about 30% or higher, preferably from about 8%to about 20%, more preferably still, from about 9% to about 18% byweight of the detergent composition. Preferred levels of nonionicdetersive surfactant herein are from about 1% to about 20%, preferablyfrom about 3% to about 18%, more preferably from about 5% to about 15%.Desirable weight ratios of anionic : nonionic surfactants in combinationinclude from 1.0:9.0 to 1.0:0.25, preferably 1.0:1.5 to 1.0:0.4.Preferred levels of cationic detersive surfactant herein are from about0.1% to about 10%, preferably from about 1% to about 3.5%, although muchhigher levels, e.g., up to about 20% or more, may be useful especiallyin nonionic cationic (i.e., limited or anionic-free) formulations.Amphoteric or zwitterionic detersive surfactants when present areusually useful at levels in the range from about 0.1% to about 20% byweight of the detergent composition. Often levels will be limited toabout 5% or less, especially when the amphoteric is costly.

[0409] The surfactant system herein is preferably present in granularcompositions in the form of surfactant agglomerate particles, which maytake the form of flakes, prills, marumes, noodles, ribbons, butpreferably take the form of granules. The most preferred way to processthe particles is by agglomerating powders (e.g. aluminosilicate,carbonate) with high active surfactant pastes and to control theparticle size of the resultant agglomerates within specified limits.Such a process involves mixing an effective amount of powder with a highactive surfactant paste in one or more agglomerators such as a panagglomerator, a Z-blade mixer or more preferably an in-line mixer suchas those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS,Lelystad, Netherlands, and Gebruder Lödige Maschinenbau GmbH, D-4790Paderbom 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferablya high shear mixer is used, such as a Lo{umlaut over (d)}ige CB (TradeName).

[0410] A high active surfactant paste comprising from 50% by weight to95% by weight, preferably 70% by weight to 85% by weight of surfactantis typically used. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the anionic surfactants used. An operatingtemperature of the paste of 50° C. to 80° C. is typical.

[0411] Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

[0412] As noted, the surfactants are used herein at levels which areeffective for achieving at least a directional improvement in cleaningperformance. In the context of a fabric laundry composition, such “usagelevels” can vary depending not only on the type and severity of thesoils and stains, but also on the wash water temperature, the volume ofwash water and the type of washing machine.

[0413] Any suitable methods for machine washing or cleaning soiledtableware, particularly soiled silverware are envisaged.

[0414] A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

EXAMPLE 13 Dichloro Manganese (II) 5,8Dimethyl-1,5,8,12-tetraazabicyclo[10.3.2]heptadecane Synthesis

[0415]

Synthesis of 1,5,9,13-Tetraazatetracyclo[11.2.2.2^(5,9)]heptadecane

[0416] 1,4,8,12-tetraazacyclopentadecane (4.00 g, 18.7 mmol) issuspended in acetonitrile (30 mL) under nitrogen and to this is addedglyoxal (3.00 g, 40% aqueous, 20.7 mmol). The resulting mixture isheated at 65° C. for 2 hours. The acetonitrile is removed under reducedpressure. Distilled water (5 mL) is added and the product is extractedwith chloroform (5×40 mL). After drying over anhydrous sodium sulfateand filtration, the solvent is removed under reduced pressure. Theproduct is then chromatographed on neutral alumina (15×2.5 cm) usingchloroform/methanol (97.5:2.5 increasing to 95:5). The solvent isremoved under reduced pressure and the resulting oil is dried undervacuum, overnight. Yield: 3.80 g, II, (87%).

Synthesis of1,13-Dimethyl-1,13-diazonia-5,9-diazatetracyclo[11.2.2.2^(5,9)]heptadecanediiodide

[0417] 1,5,9,13-tetraazatetracyclo[11.2.2.2^(5,9)]heptadecane (5.50 g,23.3 mmol) is dissolved in acetonitrile (180 mL) under nitrogen.Iodomethane (21.75 mL, 349.5 mmol) is added and the reaction is stirredat RT for 10 days. The solution is rotovapped down to a dark brown oil.The oil is taken up in absolute ethanol (100 mL) and this solution isrefluxed 1 hour. During that time, a tan solid formed which is separatedfrom the mother liquor by vacuum filtration using Whatman #1 filterpaper. The solid is dried under vacuum, overnight. Yield: 1.79 g, 11,(15%). Fab Mass Spec. TG/G, MeOH) M⁺ 266 mu, 60%, MI⁺ 393 mu, 25%.

Synthesis of 5,8 Dimethyl-1,5,8,12-tetraazabicyclo[10.3.2]heptadecane

[0418] To a stirred solution of II, (1.78 g, 3.40 mmol) in ethanol (100mL, 95%) is added sodium borohydride (3.78 g. 0.100 mmol). The reactionis stirred under nitrogen at RT for 4 days. 10% Hydrochloric acid isslowly added until the pH is 1-2 to decompose the unreacted NaBH₄.Ethanol (70 mL) is then added. The solvent is removed byroto-evaporation under reduced pressure. The product is then dissolvedin aqueous KOH (125 mL, 20%), resulting in a pH 14 solution. The productis then extracted with benzene (5×60 mL) and the combined organic layersare dried over anhydrous sodium sulfate. After filtering, the solvent isremoved under reduced pressure. The residue is slurried with crushed KOHand then distilled at 97° C. at 1 mm pressure. Yield: 0.42 g, III, 47%.Mass Spec. (D-Cl/NH₃/CH₂Cl₂) MH⁺, 269 mu, 100%.

Synthesis of Dichloro Manganese (II) 5,8Dimethyl-1,5,8,12-tetraazabicyclo[10.3.2]heptadecane

[0419] The ligand III, (0.200 g, 0.750 mmol) is dissolved inacetonitrile (4.0 mL) and is added to maganese(II) dipyridine dichloride(0.213 g, 0.75 mmol). The reaction is stirred for four hours at RT toyield a pale gold solution. The solvent is removed under reducedpressure. Sodium thiocyanate (0.162 g, 2.00 mmol) dissolved in methanol(4 mL) is then added. The reaction is heated 15 minutes. The reactionsolution is then filtered through celite and allowed to evaporate. Theresulting crystals are washed with ethanol and dried under vacuum.Yield: 0.125 g, 38%. This solid contains NaCl so it is recrystallized inacetonitrile to yield 0.11 g off a white solid. Elemental analysistheoretical: %C, 46.45, %H, 7.34, %N, 19.13. Found: %C, 45.70, %H, 7.10,%N, 19.00.

What is claimed is:
 1. A catalytic system effective for oxidation ofmaterials comprising: (a) a catalytically effective amount, preferablyfrom about 1 ppb to about 99.9%, of a transition-metal oxidationcatalyst, wherein said transition-metal oxidation catalyst comprises acomplex of a transition metal selected from the group consisting ofMn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II),Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II),Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V),Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV)coordinated with a macropolycyclic rigid ligand, preferably across-bridged macropolycyclic ligand, having at least 3 donor atoms, atleast two of which are bridgehead donor atoms; and (b) the balance to100%, preferably at least about 0.1%, of one or more adjunct materials.2. A catalytic system effective for oxidation of materials comprising:(a) a catalytically effective amount, preferably from about 1 ppb toabout 49%, of a transition-metal oxidation catalyst, said catalystcomprising a complex of a transition metal and a macropolycyclic rigidligand, preferably a cross-bridged macropolycyclic ligand, wherein: (1)said transition metal is selected from the group consisting of Mn(II),Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III),Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV),Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V),W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV); (2) said macropolycyclicrigid ligand is coordinated by at least three, preferably at least four,more preferably four or five, donor atoms to the same transition metaland comprises: (i) an organic macrocycle ring containing three,preferably four, or more donor atoms, preferably at least 3, morepreferably at least 4, of these donor atoms are N, separated from eachother by covalent linkages of at least one, preferably 2 or 3, non-donoratoms, two to five, preferably three to four, more preferably four, ofthese donor atoms being coordinated to the same transition metal in thecomplex; (ii) a linking moiety, preferably a cross-bridged chain, whichcovalently connects at least 2, preferably non-adjacent, donor atoms ofthe organic macrocycle ring, said covalently connected, preferablynon-adjacent, donor atoms being bridgehead donor atoms which arecoordinated to the same transition metal in the complex, and whereinsaid linking moiety, preferably a cross-bridged chain, comprises from 2to about 10 atoms, wherein the preferred cross-bridged chain is selectedfrom 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a furtherdonor atom; and (iii) optionally, one or more non-macropolycyclicligands, preferably selected from the group consisting of H₂O, ROH, NR₃,RCN, OH⁻, OOH⁻, RS⁻, RO⁻, RCOO⁻, OCN⁻, SCN⁻, N₃ ⁻, CN^(−, F) ⁻, Cl⁻,Br^(−, I) ⁻, O₂ ⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ²⁻, SO₃ ²⁻, PO₄ ³⁻, organicphosphates, organic phosphonates, organic sulfates, organic sulfonates,and aromatic N donors such as pyridines, pyrazines, pyrazoles,imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with Rbeing H, optionally substituted alkyl, optionally substituted aryl; and(b) the balance to 100% of one or more adjunct materials.
 3. Thecatalytic systems according to claim 1 comprising a transition-metaloxidation catalyst wherein the macropolycyclic ligand is cross-bridgedand wherein the donor atoms in the organic macrocycle ring of thecross-bridged macropolycyclic ligand are selected from the groupconsisting of N, O, S, and P, preferably N and O, and most preferablyall N.
 4. The catalytic systems according to claim 1 comprising atransition-metal oxidation catalyst wherein all the donor atoms in themacropolycyclic rigid ligand are selected from the group consisting of Nand O, and preferably all N.
 5. The catalytic systems according to claim1 comprising a transition-metal oxidation catalyst wherein themacropolycyclic rigid ligand comprises 4 or 5 donor atoms, all of whichare coordinated with the same transition metal.
 6. The catalytic systemsaccording to claim 1 comprising a transition-metal oxidation catalystwherein the macropolycyclic rigid ligand comprises 4 nitrogen donoratoms all coordinated to the same transition metal.
 7. The catalyticsystems according to claim 1 comprising a transition-metal oxidationcatalyst wherein the macropolycyclic rigid ligand comprises 5 nitrogenatoms all coordinated to the same transition metal.
 8. The catalyticsystems according to claim 1 wherein the oxidation catalyst is amonometallic, mononuclear complex.
 9. The catalytic systems according toclaim 1 comprising a transition-metal oxidation catalyst wherein atleast four of the donor atoms in the macropolycyclic rigid ligand,preferably at least four nitrogen donor atoms, form an apical bond anglewith the same transition metal of 180±50° and at least one equatorialbond angle of 90±20°.
 10. The catalytic systems according to claim 1comprising a transition-metal oxidation catalyst having coordinationgeometry selected from distorted octahedral and distorted trigonalprismatic, and preferably wherein further the cross-bridgedmacropolycyclic ligand is in the folded conformation.
 11. The catalyticsystems according to claim 1 comprising a transition-metal oxidationcatalyst wherein two of the donor atoms in the macropolycyclic rigidligand, preferably two nitrogen donor atoms, occupy mutually transpositions of the coordination geometry, and at least two of the donoratoms in the macropolycyclic rigid ligand, preferably at least twonitrogen donor atoms, occupy cis-equatorial positions of thecoordination geometry.
 12. The catalytic systems according to claim 1comprising a transition-metal oxidation catalyst which comprises one ortwo non-macropolycyclic ligands.
 13. The catalytic systems according toclaim 1 comprising a transition-metal oxidation catalyst wherein thecross-bridged macropolycyclic ligand comprises an organic macrocyclering containing at least 10 atoms, preferably from about 12 to about 20atoms.
 14. The catalytic systems according to claim 1 comprising atransition-metal oxidation catalyst wherein the transition metal isselected from manganese and iron.
 15. The catalytic systems according toclaim 1 comprising an oxygen bleaching agent.
 16. A catalytic systemeffective for oxidation of materials comprising: (a) a catalyticallyeffective amount, preferably from about 0.1 ppm to about 500 ppm, of atransition-metal oxidation catalyst, said catalyst comprising a complexof a transition metal and a macropolycyclic rigid ligand, preferably across-bridged macropolycyclic ligand, wherein: (1) said transition metalis selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III),V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II),Ru(III), and Ru(IV), and; (2) said macropolycyclic rigid ligand isselected from the group consisting of: (i) the macropolycyclic rigidligand of formula (I) having denticity of 3 or 4:

(ii) the macropolycyclic rigid ligand of formula (II) having denticityof 4 or 5:

(iii) the macropolycyclic rigid ligand of formula (111) having denticityof 5 or 6:

(iv) the macropolycyclic rigid ligand of formula (IV) having denticityof 6 or 7:

 wherein in these formulas: each “E” is the moiety(CR_(n))_(a)—X—(CR_(n))_(a′), wherein X is selected from the groupconsisting of O, S, NR and P, or a covalent bond, and preferably X is acovalent bond and for each E the sum of a+a′ is independently selectedfrom 1 to 5, more preferably 2 and 3; each “G” is the moiety(CR_(n))_(b); each “R” is independently selected from H, alkyl, alkenyl,alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R arecovalently bonded to form an aromatic, heteroaromatic, cycloalkyl, orheterocycloalkyl ring; each “D” is a donor atom independently selectedfrom the group consisting of N, O, S, and P, and at least two D atomsare bridgehead donor atoms coordinated to the transition metal; “B” is acarbon atom or “D” donor atom, or a cycloalkyl or heterocyclic ring;each “n” is an integer independently selected from 1 and 2, completingthe valence of the carbon atoms to which the R moieties are covalentlybonded; each “n′” is an integer independently selected from 0 and 1,completing the valence of the D donor atoms to which the R moieties arecovalently bonded; each “n″” is an integer independently selected from0, 1, and 2 completing the valence of the B atoms to which the Rmoieties are covalently bonded; each “a” and “a′” is an integerindependently selected from 0-5, preferably a+a′ equals 2 or 3, whereinthe sum of all “a” plus “a′” in the ligand of formula (I) is within therange of from about 7 to about 12, the sum of all “a” plus “a′” in theligand of formula (II) is within the range of from about 6, preferably8, to about 12, the sum of all “a” plus “a′” in the ligand of formula(III) is within the range of from about 8, preferably 10, to about 15,and the sum of all “a” plus “a′” in the ligand of formula (IV) is withinthe range of from about 10, preferably 12, to about 18; each “b” is aninteger independently selected from 0-9, preferably 0-5, or in any ofthe above formulas, one or more of the (CR_(n))_(b) moieties covalentlybonded from any D to the B atom is absent as long as at least two(CR_(n))_(b) covalently bond two of the D donor atoms to the B atom inthe formula, and the sum of all “b” is within the range of from about 1to about 5; and (iii) optionally, one or more non-macropolycyclicligands; and (b) the balance to 100% of one or more adjunct materials.17. The catalytic system according to claim 16 comprising atransition-metal oxidation catalyst wherein in the macropolycyclic rigidligand the D is selected from the group consisting of N and O, andpreferably all D are N.
 18. The catalytic systems according to claim 16comprising a transition-metal oxidation catalyst wherein the transitionmetal is selected from manganese and iron.
 19. The catalytic systemsaccording to claim 16 comprising a transition-metal oxidation catalystwherein in the macropolycyclic rigid ligand all “a” are independentlyselected from the integers 2 and 3, all X are selected from covalentbonds, all “a′” are 0, and all “b” are independently selected from theintegers 0, 1, and
 2. 20. The catalytic systems according to claim 16comprising a transition-metal oxidation catalyst wherein the molar ratioof transition metal to cross-bridged macropolycyclic ligand is 1:1. 21.The catalytic systems according to claim 16 wherein the oxidationcatalyst comprises only one metal per catalyst complex.
 22. Thecatalytic systems according to claim 16 comprising a transition-metaloxidation catalyst wherein in the macropolycyclic rigid ligand is amacropolycyclic moiety of formula (II) having the formula:

wherein each “a” is independently selected from the integers 2 or 3, andeach “b” is independently selected from the integers 0, 1 and
 2. 23. Thecatalytic systems according to claim 16 comprising a transition-metaloxidation catalyst wherein in the macropolycyclic rigid ligand the B isan atom selected from carbon and nitrogen.
 24. The catalytic systemsaccording to claim 16 wherein the oxidation catalyst comprises atetradentate or pentadentate cross-bridged macropolycyclic ligand. 25.The catalytic systems according to claim 16 comprising atransition-metal oxidation catalyst wherein all the donor atoms in themacropolycyclic rigid ligand are selected from the group consisting of Nand O, and preferably all N.
 26. The catalytic systems according toclaim 16 comprising a transition-metal oxidation catalyst wherein themacropolycyclic rigid ligand comprises 4 or 5 donor atoms, all of whichare coordinated with the same transition metal.
 27. The catalyticsystems according to claim 16 comprising a transition-metal oxidationcatalyst wherein the macropolycyclic rigid ligand comprises 4 nitrogendonor atoms all coordinated to the same transition metal.
 28. Thecatalytic systems according to claim 16 comprising a transition-metaloxidation catalyst wherein the macropolycyclic rigid ligand comprises 5nitrogen atoms all coordinated to the same transition metal.
 29. Thecatalytic systems according to claim 16 wherein the oxidation catalystis a monometallic, mononuclear complex.
 30. The catalytic systemsaccording to claim 16 comprising a transition-metal oxidation catalystwherein at least four of the donor atoms in the macropolycyclic rigidligand, preferably at least four nitrogen donor atoms, two of which forman apical bond angle with the same transition metal of 180±50° and atleast two of which one equatorial bond angle of 90±20°.
 31. Thecatalytic systems according to claim 16 comprising a transition-metaloxidation catalyst having coordination geometry selected from distortedoctahedral and distorted trigonal prismatic, and preferably whereinfurther the cross-bridged macropolycyclic ligand is in the foldedconformation.
 32. The catalytic systems according to claim 16 comprisinga transition-metal oxidation catalyst wherein two of the donor atoms inthe macropolycyclic rigid ligand, preferably two nitrogen donor atoms,occupy mutually trans positions of the coordination geometry, and atleast two of the donor atoms in the macropolycyclic rigid ligand,preferably at least two nitrogen donor atoms, occupy cis-equatorialpositions of the coordination geometry.
 33. The catalytic systemsaccording to claim 16 comprising a transition-metal oxidation catalystwhich comprises one or two non-macropolycyclic ligands.
 34. Thecatalytic systems according to claim 16 comprising a transition-metaloxidation catalyst wherein the cross-bridged macropolycyclic ligandcomprises an organic macrocycle ring containing at least 10 atoms,preferably from about 12 to about 20 atoms.
 35. The catalytic systemsaccording to claim 16 comprising an oxygen bleaching agent.
 36. A metalcomplex comprising manganese and a cross-bridged ligand having theformula:

wherein in this formula: each “n” is an integer independently selectedfrom 1 and 2, completing the valence of the carbon atom to which the Rmoieties are covalently bonded; each “R” and “R¹” is independentlyselected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl andheteroaryl, or R and/or R¹ are covalently bonded to form an aromatic,heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and whereinpreferably all R are H and R¹ are independently selected from linear orbranched, substituted or unsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;each “a” is an integer independently selected from 2 or
 3. 37. A metalcomplex comprising manganese and a cross-bridged ligand having theformula:

wherein in this formula “R¹” is independently selected from H, andlinear or branched, substituted or unsubstituted C₁-C₂₀ alkyl, alkenylor alkynyl.
 38. A metal complex comprising manganese and a cross-bridgedligand having the formula:

wherein in this formula: each “n” is an integer independently selectedfrom 1 and 2, completing the valence of the carbon atom to which the Rmoieties are covalently bonded; each “R” and “R¹” is independentlyselected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl andheteroaryl, or R and/or R¹ are covalently bonded to form an aromatic,heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and whereinpreferably all R are H and R¹ are independently selected from linear orbranched, substituted or unsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl;each “a” is an integer independently selected from 2 or
 3. 39. A metalcomplex comprising manganese and a cross-bridged ligand having theformula:

wherein in this formula “R¹” is independently selected from H, andlinear or branched, substituted or unsubstituted C₁-C₂₀ alkyl, alkenylor alkynyl.
 40. A method for oxidizing materials, said method comprisingcontacting, preferably in the presence of a liquid, a material capableof being oxidized with an oxidation agent and a transition-metaloxidation catalyst, wherein said transition-metal oxidation catalystcomprises a complex of a transition metal selected from the groupconsisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV),Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV)coordinated with a macropolycyclic rigid ligand, preferably across-bridged macropolycyclic ligand, having at least 3 donor atoms, atleast two of which are bridgehead donor atoms.
 41. The method accordingto claim 40 wherein the material capable of being oxidized is selectedfrom organic functional groups, hydrocarbons, and heteroatoms,preferably alkenes, sulfides, oxidizable dyes, oxidizable stains,woodpulp and oxidizable effluents.
 42. The method or compositionsaccording to claim 1 wherein the oxidation agent is selected from thegroup consisting of sodium hypohalites, preferably hypochlorite,hydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates,organic peroxyacids, organic hydroperoxides, monopersulfates, andmixtures thereof.
 43. The method according to claim 40 wherein thetransition-metal oxidation catalyst is selected from the Mn(II), Fe(II)and Cr(II) or the corresponding oxidation state (III) complexes, of aligand selected from:

wherein p is 1 and m and n are 1 or m is 0 and n is from 1 to 3 and A isa nonhydrogen moiety, preferably selected from methyl, ethyl and propyl;and


44. A metal complex comprising a transition metal selected from Mn, Feand Cr, preferably Mn, and a cross-bridged ligand having the formula:

wherein m and n are integers from 0 to 2, p is an integer from 1 to 6,preferably p is 1 and preferably m and n are both 0 or both 1,preferably both 1, or m is 0 and n is at least 1; and A is a nonhydrogenmoiety, preferably having no aromatic content.
 45. The metal complexaccording to claim 44 wherein each A is independently selected frommethyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C5-C20alkyl, and one, but not both, of the A moieties is benzyl, andcombinations thereof.
 46. A metal complex comprising a transition metalselected from Mn, Fe and Cr, preferably Mn, and cross-bridgedmacropolycyclic ligands having the formula:

wherein “R¹” is independently selected from H, and linear or branched,substituted or unsubstituted C₁-C₂₀ alkyl, alkylaryl, alkenyl oralkynyl, and preferably R¹ is selected from alkyl or alkylaryl; andpreferably all nitrogen atoms in the macropolycyclic rings arecoordinated with the transition metal.
 47. A metal complex comprising atransition metal selected from Mn, Fe and Cr, preferably Mn, andcross-bridged macropolycyclic ligands having the formula:

wherein: each “n” is an integer independently selected from 1 and 2,completing the valence of the carbon atom to which the R moieties arecovalently bonded; each “R” and “R¹” is independently selected from H,alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or R and/or R¹are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,or heterocycloalkyl ring, and wherein preferably all R are H and R¹ areindependently selected from linear or branched, substituted orunsubstituted C₁-C₂₀ alkyl, alkenyl or alkynyl; each “a” is an integerindependently selected from 2 or 3; and preferably all nitrogen atoms inthe macropolycyclic rings are coordinated with the transition metal. 48.A metal complex comprising a transition metal selected from Mn, Fe andCr, preferably Mn, and cross-bridged macropolycyclic ligands having theformula:

wherein in either of these formulae, “R¹” is independently selected fromH, or, preferably, linear or branched, substituted or unsubstitutedC₁-C₂₀ alkyl, alkenyl or alkynyl; and preferably all nitrogen atoms inthe macropolycyclic rings are coordinated with the transition metal. 49.A method for synthesizing a manganese-containing metal complex accordingto claim 44, wherein the catalyst is prepared under strictly oxygen andhydroxyl-free conditions by reaction of bis(pyridine) manganese (11)salts, preferably the chloride salt, with a cross-bridgedmacropolycyclic ligand having the formula of the metal complex.